ISBN 1895198097
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Malkin, Aleksandr Yakovlevich
Rheology fundamentals
(Fundamental topics in rheology)
Includes bibliographical references and index
ISBN 1895198097
1. Rheology . Title. II. Series
QC189.5.M35 1994 531'.11 C959000003
Content
1 Introduction. Rheology: subject and language 1
2 Stresses 9
2.1 General theory 9
2.2 Law of equality of conjugated shear stresses 13
2.3 Principal stresses 13
2.4 Invariants 16
2.5 Hydrostatic pressure and deviator 18
2.6 Equilibrium (balance) equations 21
2.7 Examples 24
2.7.1 A bar loaded by the constant force 24
2.7.2 A bar loaded by its own weight 25
2.7.3 Sagging of a flexible bar or a fiber 25
2.7.4 Internal pressure in a thinwalled cylinder 26
2.7.5 Hemispherical membrane under its own weight 28
2.7.6 Torsion of a thinwalled cylinder 29
2.7.7 Torsion of a cone over a plate 29
2.7.8 Stresses in a media moving along a cylinder 30
2.7.9 Stresses around a circular hole in a sheet 31
2.8 Concluding remarks 32
2.9 References 33
3 Deformation and deformation rate 35
3.1 Displacements and deformations 35
3.2 Deformation rate 39
3.3 Large deformations 41
3.4 Principal values and invariants of the deformation tensors 45
3.5 Uniaxial elongation. Poisson ratio 47
3.6 Simple shear and pure shear 49
3.7 Examples 53
3.7.1 Uniaxial extension of a bar (beam, fiber) 53
3.7.2 Shear 54
3.7.3 Plane deformation (strain) state 55
3.7.4 Threedimensional deformed state 56
3.8 Concluding remarks 57
3.9 References 58
4 Rheological equations of state 61
4.1 Main rheological effects 61
4.1.1 NonNewtonian viscosity 62
4.1.2 Plastic behavior 68
4.1.3 Weissenberg effect 70
4.1.4 Transient deformations in shear (of liquids) 74
4.1.5 Uniaxial extension 76
4.1.6 Instabilities and secondary flows 78
4.1.6.1 Extrudate distortions (melt fracture) 81
4.1.6.2 Secondary flow 84
4.1.6.3 Waving in extensional flows 89
4.1.6.4 Interfacial and surface instability 90
4.1.6.5 Rheological phenomenon in inertial turbulence (Toms effect) 91
4.1.7 Thixotropy and rheopexy 95
4.1.8 Nonlinear elasticity 97
4.1.9 Viscoelastic behavior 101
4.1.10 Flow around solid obstacles 104
4.1.11 Phase transitions induced by deformations 105
4.2 General principles 106
4.3 Concluding remarks 111
4.4 References 115
5 Rheological viscous fluids 119
5.1 Definitions 119
5.2 Newtonian liquid 122
5.3 NonNewtonian liquids 126
5.4 Viscoplastic liquids 130
5.5 Some basic problems 131
5.5.1 Introduction 131
5.5.2 Plane unidimensional flow 133
5.5.3 Flow through straight tubes under pressure 149
5.5.4 Penetration of a cylinder into a viscous medium 156
5.5.5 Resistance to rotation of a thin disk in a liquid 162
5.5.6 Converging (diverging) flows 164
5.5.7 Movement of a ball through a viscous fluid 169
5.5.8 Compression of a liquid between two parallel disks 174
5.5.9 Hydrodynamics of rolling 178
5.5.10 Flow in lubricant layer 180
5.6 Concluding remarks 183
5.7 References 185
6 Elastic solids 187
6.1 Definitions 187
6.2 Hookean elastic material 189
6.3 Linear anisotropic materials 196
6.4 Large elastic deformations in solids 197
6.5 Limits of elasticity 208
6.6 Some basic problems 211
6.6.1 General formulation 211
6.6.2 Uniaxial extension 212
6.6.3 Bending by a torque 215
6.6.4 Bending by a transverse force 218
6.6.5 Torsion of a bar 226
6.6.6 Temperature stresses 230
6.6.7 Cylinder under internal pressure 231
6.6.8 Pressure inside a sphere 233
6.6.9 Stresses and deformations in membranes 234
6.6.10 Contact (local) stresses 238
6.7 Concluding remarks 241
7 Viscoelasticity 245
7.1 Introduction 245
7.2 Definitions 248
7.2.1 Creep 248
7.2.2 Relaxation 249
7.2.3 Periodic oscillations 250
7.3 Principle of superposition 258
7.4 Relaxation and retardation spectra 262
7.4.1 Calculation of continuous spectrum 264
7.4.2 Calculating discrete spectrum 265
7.5 Dynamic and relaxation properties  correlations 268
7.6 Relationships between constants 272
7.6.1 Viscoelastic solid 273
7.6.2 Viscoelastic liquid 274
7.7 Mechanical models of viscoelastic behavior 274
7.8 Superposition 281
7.9 Applications of linear viscoelasticity 286
7.9.1 Comparison of materials by their viscoelastic properties 286
7.9.2 Calculation of the response 291
7.10 Nonlinear viscoelasticity. Introduction 294
7.10.1 Large deformations in nonlinear viscoelasticity 296
7.10.2 Relaxation properties dependent on deformation 300
7.11 Concluding remarks 304
7.12 References 307
Nomenclature 309
Subject index 317
1
INTRODUCTION
RHEOLOGY:
SUBJECT AND LANGUAGE
Rheology as an independent branch of natural sciences emerged more than 60
years ago. Its origin was related to observation of “strange” or abnormal behav
ior of many wellknown materials and difficulty in answering some very “sim
ple” questions. For example:
• paint is evidently a liquid because it canbe poured into a bottle, but why does
it remain on a vertical wall without sagging down, like any other liquid?
• a colloid solution is a liquid, but why does viscosity of such a liquid, in con
trast to other liquids, appear different when we measure it under varying
conditions of flow?
• clay looks quite like a solid but everybody knows that it canbe shaped; it also
takes the formof a vessel like any liquid does; if clay is a solid, why does it be
have like a liquid?
• yogurt in a can is rather thick (its viscosity is high) but after intensive mix
ing its viscosity decreases, to increase again when left to rest, so which value
of viscosity should be considered?
• concrete looks quite solidandrigid, but whensubjectedto anexternal force it
changes its dimensions (and shape) like liquid; which are the reasons for
such a behavior?
A. Ya. Malkin 1
• parts made out of polymeric materials (plastics) look rather solid and hard,
quite similar to parts made out of metal, but they are noticeably different.
When a force is applied to a metallic part it will slightly change its shape and
will maintain its newshape for a long time. This is not the case with plastics
which also change their shape after a force is applied but which continue to
change shape. If this material is solid, why does it “stalk”?
• pharmaceutical pastes (for example, toothpaste or a body paste) must be
“liquid” to be smoothly applied and not too “liquid” to remain on the skin; are
all these pastes liquids or not?
• sealants widely used in construction must be fluidlike to close (to seal) all
spaces (joints) and to fill cavities, but then sealant must rapidly “solidify” to
prevent its flow out of these spaces; is sealant liquid or not?
These examples can easily be extended. The general feature of all these exam
ples is that they are relevant to many real materials and they all exhibit very
complicated superimposition of liquidlike and solidlike properties. It means
primarily that commonlyused words “liquid” and “solid” are insufficient and we
need to introduce a newterminology as a result of understanding particular fea
tures of behavior and properties of all the abovementioned and many other ma
terials. Moreover, we need newmethods to measure and characterize properties
of real materials quantitatively and in adequate terms.
The next common feature of all these newlydiscussed phenomena is the exis
tence of time effects, i.e., the results of observations depend on a time scale.
Certainly time by itself has no sense, and the appearance of time effect means
that something happens to a material in an experimental time scale. In general,
time is a reflection of changes in material structure taking place during the pe
riod of observation (or experiment).
Thus, rheology is a branch of natural sciences considering real materials with
changing structure. Certainly any natural science pretends to deal with reality
and does it by means of phenomenological models. Any model is created to
reflect not all, but the most important, characteristic features of an object. The
ideas of a liquid and a solid are also models and their formal (mathematical)
representation originated from the classical works of Isaac Newton and Robert
Hooke.
Newton
1
reflected upon a resistance of liquid to a cylinder rotating in a vessel.
His ideas were converted to a more accurate form by Stokes,
2
who formulated a
general law of liquidlike behavior, now named the Newton  Stokes Law:
2 Introduction
σ ηγ = & [1.1]
whereσ is shear stress, and & γ is rate of deformation. The exact rigorous meaning
of these terms will be discussed below, but now, in order to be brief, we can say
that this lawassumes that a force (or resistance) is proportional to a velocity (of
movement). The coefficient of proportionality, η, is called viscosity (or coeffi
cient of viscosity).
Hooke
3
formulated a similar proposal concerning properties of solids. The law,
named after him, was translated to modern form by Bernoulli, and the Hooke
Law states that stress, σ
E
, is proportional to deformation, ε :
σ ε
E
= E [1.2]
The coefficient of proportionality is called the Young modulus, E. Again the
formal meaning of these values will be discussed below, but briefly, the Hooke
Law says that the force is proportional to the displacement.
Both models represent properties of many real materials and work well in de
scribing their behavior with considerably high degree of accuracy. However,
there are numerous other real materials which are not described by the
abovementioned Newton  Stokes and Hooke laws. Rheology relies on the idea
that nonNewtonian and nonHookean materials exist in reality. These
materials are interesting from both theoretical and applied aspects, and that is
why such materials must be the objects of investigation. Indeed, the abovecited
examples show that a great number of materials used in engineering practice
and in everyday life are “strange” and “abnormal” fromthe point of viewof clas
sical concepts of liquid and solid materials.
This can be treated as the definition of rheology: it is a science dealing with
materials having properties not described by models of Newton  Stokes and
Hooke. It is a negative statement (the rule of contraries). The positive statement
says that rheology studies materials having properties described by any rela
tionship between force and deformation. In this sense, the Newton  Stokes and
Hooke Laws are limiting cases formally lying on the border of rheology.
It is important to emphasize again that every model describes (represents)
properties of real materials with a different degree of approximation. The New
tonStokes and Hooke laws appeared to be insufficiently accurate for many in
A. Ya. Malkin 3
dustrial materials, which is why rheology, with its more strict and complex laws
and equations, gave much better approximation of reality than the classical
Newton  Stokes and Hooke laws known to everybody from his schoolyears.
Both phenomenological laws (i.e., taken as probable assumptions, but only as
sumptions) avoid the problemof the inherent structure of matter. Almost every
body is convinced that matter consists of molecules and intermolecular empty
space, which means that in reality, any material body is heterogeneous. At the
same time, any observer is sure that he sees a body of matter as a homogeneous
continuous mass without holes and empty spaces. The obvious way out of these
contradictory evidences lies in the idea of the space scale of observation.
This scale must be large enough to distinguish individual molecules or their
segments. Characteristic size of a molecule (its crosssection or length of several
bonds) is 1 nm. Then, only when one deals with sizes of the order of 10 nm, can
one neglect molecular structure and treat a body as homogeneous. It means that
a characteristic volume is of an order larger than 10
3
nm
3
. This is a real size of a
physical “point”; which is quite different from a philosophical or geometrical
point, the latter is an infinitely small object of zerosize. The physical “point”
contains ≈10
4
molecules or segments of macromolecule, and throughout its vol
ume all molecularsize fluctuations are averaged. The number of molecules in
such a point is large enough for smoothing and averaging procedures.
Having in mind the real scale of a physical point, we think that we have a right
to apply methods of mathematical analysis of infinitesimal quantities (whichre
late to a geometrical point) to a physical medium. The formal extrapolation of
physicsbased analysis to infinitely small sizes tacitly avoids the incorrectness
of this operation, and the only justification for this is the fact that in almost all
practical applications, nobody is interested in what really happens in a very
small volume.
There are at least two important principle exceptions:
• firstly, a central physical problem exists in explanation of observed
macrofacts on the base of the molecular structure of matter. In this ap
proach, one would like to understand what happens to a molecule or how
intermolecular interactions occur; then going through microvolumes con
taining numerous molecules and averaging molecular phenomena, one
would come to the macroproperties of a body.
• secondly, in some applications we meet with “zero” size, if geometrical
shapes under consideration have angles and the size at the corner of any an
4 Introduction
gle is (formally) equal to zero. Extrapolation of calculation results to such
zero volumes sometimes leads to infinite values, and this is out the realm of
physical meaning. That is why analysis of problems of this kindrequires spe
cial methods.
Pertinent to the above discussion, we shall consider homogeneous continuous
media, and both adjectives concern a size less than conditionally ≈10 nm. In
larger scales, a body can have structure and be heterogeneous. For example, a
body can be a mixture of some components with steplike transitions between
them. Avery typical example of suchheterogeneity is a filled polymeric material
(e.g., plastics with mineral filler) where a filler forms a statistical or quite well
arranged (in reinforced plastics) structure. In some applications we may not be
interested in this structure and continue to treat the medium as homogeneous,
averaging inner differences up to much higher scales (for example for many as
tronomic observations, the sun and our Earth are quite homogeneous and more
over can be treated as “points”). In other cases, the role of heterogeneity can be
important and even a determining factor (for example, for reinforced plastics),
but, inany case, the scale of suchheterogeneity has to be muchlarger thanchar
acteristic molecular sizes.
Considering all the abovementioned limitations and the physical meaning of
terms which have been and will be used, let us formulate the main problem of
rheology. We have already tried to do it from a different perspective, and with
the present background we are able to add some additional details to the discus
sion.
Rheology studies behavior of various real continuous media. What do we
mean saying “behavior”? For a body of finite size, it is a relationship between
outer action(forces, appliedto a body) andinner reaction(changes of a shape of a
body). For the continuous media we can extrapolate this approach to a point and
examine the relationship between forces at this point and deformation, i.e.,
change of a distance between two arbitrary points in a body.
Thus when we consider what happens in a body in a point of reference, we
avoid the problem of a geometrical form of a body as a whole and are interested
only in its substantial, inherent properties. Now we come to a definition of the
subject of rheology: it is determination of mechanical properties of continuous
media having a different nature, i.e., ascertaining relationships between forces
and movements of a matter “in a point of reference”.
In its origin, the term “rheology” has been related to flowing media, since the
A. Ya. Malkin 5
main root of the word means “to flow” (rheo in Greek). Currently, the term is
used for any real material because sometimes it is very difficult to estimate
whether a material is solid or fluid. As a result, the analytical methods used for
both classes of media are very similar.
The place of rheology among other natural sciences and applied problems is
shown in Figure 1.1. One can see that rheology is a multidisciplinary science
having many points of relationship with fundamental physics and chemistry, as
well as having applications to real technological and engineering materials in
life.
To recapitulate, it seems useful to point out the main ideas of the Introduction
insofar as they will allow us to compose a dictionary of Rheology.
Rheology is a science concerned with mechanical properties of various
6 Introduction
Figure 1.1. Rheology  its place among other sciences considering applied problems.
solidlike, liquidlike, and intermediate technological and natural products (ma
terials). It accomplishes its goals by means of models representing principle pe
culiarities of behavior of these materials. The behavior of a material is a
relationship between forces and deformations (or changes of shape) and a
model gives a mathematical formulationof the relationship, rheological prop
erties being expressed by the structure of a model (i.e., its mathematical image)
and values of constants included in a model — characteristic for a material.
Rheological models are related to a point, which is a physical object including
a sufficient number of molecules in order to neglect the molecular structure of
matter and to treat it as continuum. The rheological analysis is based on the
use of continuum theories, meaning that the following is assumed:
• there is no discontinuity in transition fromone geometrical point to another,
and the mathematical analysis of infinitesimal quantities can be used; dis
continuities appear only at boundaries
• properties of material can change in space (due to the gradient of concentra
tion in multicomponent mixtures, temperature distribution or other rea
sons) but such change occurs gradually; these changes are reflected in space
dependencies of material properties entering equations of continuum theo
ries which must be formulated separately for any part of material sur
rounded by the boundary surfaces at which discontinuity takes place
• continuity theories include an idea of anisotropy of properties of a material
along different directions.
Rheological behavior of a material depends ontimeandspace scales of obser
vation (experiment). The former is important as a measure of the ratio of the
rate of inherent processes in a material to the time of experiment and/or obser
vation; the latter determines the necessity to treat a material as homo or heter
ogeneous.
Rheological properties of a material can be understood via balance (or conser
vation) equations (equations of solid state continuumor fluid dynamics), being a
methodto transit fromproperties at a point to anobservedbehavior of anitemor
a medium as a whole.
The results of macroscopic description of behavior of real engineering and bio
logical media, based ontheir rheological properties, are used innumerous appli
cations related to technology of synthesis, processing, and shaping of different
materials (plastics and ceramics, emulsions and dispersions inthe chemical and
food industries, pharmaceuticals, cosmetics, transport, oil industry, etc.), their
A. Ya. Malkin 7
longterm properties, natural phenomena, such as movement of mud streams
and glaciers, and biological problems (dynamics of blood circulation, work of
bones). One can conclude that the first goal of rheology is a search for stress ver
sus deformationrelationships for various technological and engineering materi
als in order to solve macroscopic problems related to continuum mechanics of
these materials.
The second goal of rheology consists of establishing relationships between rhe
ological properties of a material and its molecular composition content. It is an
important independent problem related to estimating quality of materials, un
derstanding laws of molecular movements and intermolecular interactions. The
termmicrorheology, relatedto classical works by Einstein,
4
devotedto viscous
properties of suspensions, is sometimes used in this line of thought, and it
means that the key interest is devoted not only to movements of physical points
but also to what happens inside the point during deformation of a medium.
REFERENCES
1. I. Newton, Principia, Section IX of Book II, 1684.
2. G. Stokes, Trans. Camb. Phil. Soc., 8, 287 (1845); Math. Phys. Papers, 1, 75 (1880).
3. R. Hooke, Lecture de Potentia Restitutiva, London, 1678.
4. A. Einstein, Ann. Physik, 19, 289 (1906); 34, 591 (1911).
8 Introduction
2
STRESSES
2.1 GENERAL THEORY
Any external actionappliedto a body leads either to a movement of a body inits
entirety or to a deformation of its initial shape, or perhaps to both results simul
taneously. The first consequence of an external action  the movement of a body
in space or its rotation around its center of gravity, without any changes to its
shape  is a subject of study by mechanics, and as such it is not relevant for us in
this book. Only what happens inside a body is of principle subject of our discus
sion.
Briefly speaking, it means that we must consider two possibilities:
• a dynamic situationinwhichwe needto analyze the result of external forces
• a geometric and/or kinematic situation in which it is important how and at
which speed distances between different points of a body change, or how lo
cal shapes (conditionally drawn inside a body) distort.
Dynamic situation in any point of a medium is expressed by a physical quan
tity called stress.
Aninitial projectionof stress is very simple and obvious. Let us consider a body
(bar). The area of its normal section is S (Figure 2.1). The force, F, acts normal to
the surface, S. The specific force at any point of the sectionis equal to F/Sand is a
normal stress or tensile stress:
σ
E
= F S [2.1]
A. Ya. Malkin 9
i.e., stress is a force related to the unitary surface area.
The force at a free surface may not be constant but distributed, i.e., be a func
tion of coordinates. For example, a train moving along the rails presses on them
at several local zones (where wheels toucha rail), i.e., a force is distributed along
a rail and as a result a very complex pattern of stresses acting in the body of a
rail appears. In this case, we can mark a small area, ∆S, to find a relative (spe
cific) force acting on the area ∆ ∆ F S. If we decrease the surface area, we even
tually come to the limit of the ratio ∆ ∆ F Sat ∆S 0 → and this limit is a normal
stress at the marked point:
σ
E
S 0
= lim( F S) = dF dS
∆
∆ ∆
→
This formula shows clearly that the stress is related to a point and can change
from point to point.
We canalso imagine a different situationwhere the force Tacts not normal but
tangential to the surface as shown in Figure 2.2. If the area of the surface is S,
then the tangential or shear stress is equal to T/S, or
σ = T S [2.2]
These simple and obvious relations must be generalized to an arbitrary orien
tationof anapplied force. One may ask: what are the stresses acting ona surface
with any orientation in respect to force? The problem can be solved by two vec
tors: of force, F, and orientation of a surface; the latter is characterized by nor
mal, n, to surface (Figure 2.3).
10 Stresses
Figure 2.1. A bar loaded by a normal force. Figure 2.2. Shear of matter.
We knowthat there are phys
ical concepts which can be pre
sented by one quantity only,
such as density of a matter, for
example. Such objects are
called scalars. There are
physical characteristics which
must be defined not only by
their size but also by a direc
tion of their action; such as ve
locity, for example, and not one
but three quantities  projec
tions of velocity along three coordinate axes  are necessary to determine veloc
ity. Such physical objects are called vectors.
We deal with stresses. For their complete characterization it is necessary to
knownot only the value of a force acting at a point (this force is a vector by itself)
but also its orientation in respect to a surface to which this force is applied (and
orientation is also presented by a vector). It means that for complete character
ization of a stress we need to know two vectors: of a force and a normal to a sur
face to whichthis vector is applied. The physical objects whichare determinedin
such a manner are called tensors, and that is why stress is a tensor.
Any vector can be represented by its three projections along the orthogonal co
ordinate axes:
n = n(n
1
, n
2
, n
3
)
F = F(F
1
, F
2
, F
3
)
Then the nine values can be constructed: three projections of F on surfaces de
termined by any of the three coordinate vectors. As the area of a surface is not es
sential, all values of F
i
(i = 1, 2, 3) must be divided by the area which gives
components of a stress tensor, σ
ij
, where the first index shows the orientationof a
force and the second index designates the orientation of a surface.
The result is written in the form of a table (matrix)
A. Ya. Malkin 11
Figure 2.3. Force vector, F, and orientation of a sur
face, n.
σ
σ σ σ
σ σ σ
σ σ σ
ij
11 12 13
21 22 23
31 32 33
=








where the first column represents components of a force (of a vector of a force)
applied at the plane normal to the x
1
axis, the second column gives the same for
the x
2
axis andthe thirdto x
3
axis. The directions of the normals are indicatedby
the second indices. The table within the bars is the set (or a list) of all compo
nents (projections) of a force vector applied on differently oriented planes at an
arbitrary point inside a body. In order to emphasize that this set of parameters
presents a single physical object  stress tensor  it is usual to put thembetween
the bars.
The picture which shows all components of
a stress tensor acting at a point is drawn in
Figure 2.4. One can easily see that compo
nents with the same numbers in the index
are normal stresses, quite equivalent to the
initial definition of the normal stress in Eq
2.1, and all values with different numbers in
the index are shear stresses, as in Eq 2.2.
All components of the stress tensor are de
termined at a point and can be constant or
variable in space (inside a medium). It de
pends on configuration of outer forces ap
plied to a body. For example, the force field is
homogeneous for the situation shown in Fig
ure 2.1 and in this case a stress tensor is con
stant (inside a body). But the stress field (or
stress distribution) appears to be very com
plicated inmany other cases, for example ina
liquid flowing inside a channel or in a case of roof covered with snow. Some other
examples illustrating stress distributions will be discussed at the end of this
Chapter.
There are some fundamental facts concerning the stress tensor (and any other
tensors as well) and they will be discussed below.
12 Stresses
Figure 2.4. Definition of the compo
nents of the stress tensor.
2.2 LAW OF EQUALITY OF CONJUGATED SHEAR STRESSES
Let us consider a plane sectionof a unit cube inFigure 2.4. The sectionis shown
inFigure 2.5. The rotational equilibriumconditionabout the central point of the
square gives the equality
σ σ
12 21
·
The same is true for any other pair of
shear stresses:
σ σ σ σ
13 31 23 32
· · ;
These equalities are known as the
Cauchy rule:
1
σ σ
ij ji
=
The result means that only three in
dependent shear components of the
stress tensor exist, and the stress state
at a point is completely defined by six
independent values; three normal
(σ σ σ
11 22 33
, ,and ) and three shear stresses (σ σ σ σ σ σ
12 21 13 31 23 32
= , = ,and = ).
2.3 PRINCIPAL STRESSES
The idea of principal stresses (max
imal and minimal) appears as a con
sequence of the dependence of
stresses on orientation of a surface.
Let us illustrate it by two simple ex
amples generated from Figures 2.1
and 2.2.
The normal stress, σ
E
, is calculated
as in Eq 2.1. The following question
A. Ya. Malkin 13
Figure 2.5. Plane stress state.
Figure 2.6. Decomposition of the normal force
at the arbitrary oriented surface.
needs to be answered: if the force equals Fas before, what are the stresses acting
at the surface inclined to the vector Fat the angleα (Figure 2.6)? It is easily seen
that the vector F can be decomposed into normal F
n
and tangential F
σ
compo
nents to the surface aa, i.e., there are normal and shear stresses at this surface.
The area of this surface is S/sinα, meaning that normal, σ
α E,
, and shear, σ
α
,
stresses (forces divided by the surface area) depend on α and are equal to
σ α
α
σ α
α E
n
F
S
F
S
,
sin
sin
sin · · ·
2
2
σ α
α α σ
α
α
σ
· · ·
F
S
F
S
sin
sin cos
sin
2
2
There are some interesting and peculiar orientations in a body:
at α = 90
o
σ
E
= max and σ = 0 (the later is evident from Figure 2.1);
at α ·45
o
σ σ = 2= max
E
at α ·0 σ
E
= 0 and σ ·0 (plane free of stresses).
Figure 2.7 allows one to analyze the situationsim
ilar to the picture shown in Figure 2.2. Let the area
of both sides of a cube be equal to a unit, so σ is a
shear stress. In this case we can write the following
equations for σ σ
α α E,
and :
σ σ α α σ α
α E,
= 2 cos sin = sin2
σ σ α α σ α
α
= (cos sin ) = cos 2
2 2
−
Again there are some peculiar orientations:
at α ·0 σ
α E,
= 0 and σ σ
α
=
at α ·45
o
σ σ
α E,
= = max and σ
α
·0
at α ·90
o
σ
α E,
= 0 and σ σ
α
=
(equivalence at α α = 0and = 90
o
is the consequence of the Cauchy rule).
14 Stresses
Figure 2.7. Projections of
the shear stress at an arbi
trary oriented surface.
The discussionshows that, infact, at any arbitrary orientation(or direction) in
a body, both normal and shear stresses can exist irrespective of simple pictures
with only normal (Figure 2.1) or only shear (Figure 2.2) stresses. Moreover,
there are always directions where either normal or shear stresses are maximal.
The last result is very important because various media resist application of ex
tension (normal force) or shear (tangential force) in different manner.
For example, it is very difficult to compress a liquid (compression is an action
equivalent to applicationof negative normal stresses) but it is very easy to shear
a liquid (to move one layer relative to another like cards in a pile). Another case:
when a thin filmis stretched (it can be a cover of a balloon stretched by the inner
gas pressure), it breaks as a result of anactionof normal stresses, whereas shear
stresses are practically negligible in this case.
The abovediscussed examples are only illustrations of a general idea that all
components of a stress tensor depend on orientation of a surface, for which one
wants to calculate them. It is a result of projecting a vector along different direc
tions: the size of a projection depends on orientation of the axes in space.
There are general rules and equations for calculating components of the stress
tensor at any direction, generalizing equations written above for σ
α E,
and σ
α
.
The main interest and the result of all these calculations and discussions are
connected with the existence of such direction in a body where stresses are
extremal. Theoretical analysis shows that for any arbitrary stress tensor it is
possible to find three orthogonal, i.e., perpendicular to each other, directions, at
which normal stresses are extremal and shear stresses are absent. Examples of
such situations have been shown above for the cases drawn in Figures 2.6 and
2.7. Indeed, normal stressesσ
ii
=max at these directions at whichshear stresses
are absent, σ
ij
=0. These normal stresses are called principal stresses. The ex
istence of principal stresses is a general law for any stress tensor.
The concept of principal stresses allows one to find a minimal number of pa
rameters which completely characterize the stress state at any point. It is im
possible to compare stress states at different points of a body or in different
bodies if only operating with six independent components of the stress tensor
acting along different directions. It is much easier to do so dealing with only
three normal stresses. For example, one canexpect that some materials are rup
tured by an action of a normal stress if it reaches a critical level, that is why it is
important to knowthe value of maximal normal stress acting in a material, and
this maximal stress is the principal stress.
A. Ya. Malkin 15
2.4 INVARIANTS
If we cancalculate principal stresses, it means that we canrepresent the stress
state of matter by three independent values, and every different stress state is
equivalent if principal stresses are the same for all of them. This means, in par
ticular, that various physical phenomena taking place under stress (for exam
ple, probability for a “quasiliquid” to stick to a vertical wall and stay motionless
in spite of action of gravitational force; rupture of solid bodies; slow movement
and transition to spurt for snow, sand or mud on slopes, etc.) can be considered
as a consequence of an action of principal stresses only.
Principal stresses represent stress state ina body (at a givenpoint), regardless
of any possible set of normal and shear stresses at any arbitrary orientation of
this point. In other words, they are invariant in respect to the choice of orienta
tion. Then the question is: how to calculate principal stresses if all components
of the stress tensor are known for some arbitrary coordinate system? Theory of
tensors gives an answer to this question in the form of a cubic algebraic equa
tion:
σ σ σ
3
1
2
2 3
I + I I = 0 − − [2.4]
and principal stresses are three roots of this equation designated asσ σ σ
1 2 3
, , . It
is clear that the roots are expressed through coefficients of Eq 2.4, I
1
, I
2
, and I
3
.
These coefficients are constructed by means of all components of stress tensor
for arbitrary orthogonal orientations in space as:
I = + +
1 11 22 33
σ σ σ [2.5]
I = + + ( + + )
2 11 22 11 33 22 33 12
2
23
2
13
2
σ σ σ σ σ σ σ σ σ − [2.6]
I = + 2 ( + + )
3 11 22 33 12 23 13 11 23
2
22 13
2
33 12
2
σ σ σ σ σ σ σ σ σ σ σ σ − [2.7]
As the roots of Eq 2.4, theσ σ σ
1 2 3
, ,and do not depend on orientation of axes of
a unit cube (at a point) in space, on one hand, and they are expressed through
values of I
1
, I
2
, and I
3
, on the other. This leads to the conclusion that I
1
, I
2
, and I
3
are also invariant in respect to the choice of directions of orientation and that is
why they are usually calledinvariants of a stress tensor at a point. According to
its structure (the power of components), I
1
is a linear, I
2
is a quadratic, and I
3
is a
cubic invariant.
16 Stresses
Certainly any combination of the invariants, I
1
, I
2
, and I
3
, is also invariant in
respect to the orientationof axes inspace. Various elegant or cumbersome struc
tures of invariants are possible to be built but it is important to knowthat three
and only three independent values of such kind do exist.
Invariants are characteristics of the physical state of a matter. It means that
neither any stress by itself nor its arbitrary combination but only invariants de
termine a possibility of occurrence of various physical effects such as, for exam
ple, phase transitions, storage of elastic energy or dissipation (transition to
heat) of work of external forces. There is a fundamental principle saying that
physical effects must be independent of choice of a coordinate system and that is
why invariants, which are values independent of a coordinate system, govern
physical phenomena occurring due to application stresses.
In many practical problems, we deal a with twodimensional or sonamed
plane stress state. The very typical example of it are thinwalled items with
stressfree outer surfaces. “Thin” means that the size in direction normal to the
surface is much smaller than other two dimensions. Stresses in planes parallel
to the free surfaces can be assumed to be absent in comparison with stresses at
two other oriented planes. This can be proven by a pure geometrical argument:
because stresses are zero onbothfaces, they might not vary appreciably over the
small distance (thickness of the item).
In the plane stress state, all the components containing the index “3" vanish
and the full stress tensor looks like this:
σ
σ σ
σ σ
ij
11 12
21 22
=
0
0
0 0 0








[2.8]
In this case, one principal stress, σ
3
, is zero and two others, σ σ
1 2
and , are the
roots of a quadratic (but not cubic) algebraic equation:
σ
σ σ σ σ
σ
1,2
11 22 11 22
2
12
2
=
+
2 2
+
1
2
t
− 
.
`
,
¹
'
¹
¹
¹
¹
'
¹
¹
¹
Typical examples of thin (or twodimensional) elements are various balloons,
A. Ya. Malkin 17
membranes and covers, barrels and tanks, and so on. And for all these articles
and many others, we can use the analysis of the twodimensional (or plane)
stress state.
There are two particularly simple cases of the plane stress state, which are
simple (or unidimensional) tension and simple shear. In fact, these cases were
mentioned at the very beginning of this chapter, and their tensorial nature is il
lustrated by the abovediscussed Figures 2.6 and 2.7 and rules of a transforma
tion of stress components with rotation of coordinate axes.
2.5 HYDROSTATIC PRESSURE AND DEVIATOR
It seems quite obvious that only nor
mal stresses can change the volume of
a body, while shear stresses distort its
form(shape). For this reasonit appears
to be reasonable to divide a stress ten
sor into two components, singling out
the components connected to action of
the normal stresses.
Let us consider the situation of alldi
rection compression of a body under
pressure, p (Figure 2.8). This case is
called hydrostatic pressure. The main
feature of hydrostatic pressure is the
absence of shear stresses; hence, all
components of the matrix except nor
mal are equal to zero and the stress
tensor for this case looks like this:
σ
ij
=
p 0 0
0 p 0
0 0 p








[2.9]
i.e., all principal stresses are the same and equal to p:
σ σ σ
1 2 3
= = = p −
18 Stresses
Figure 2.8. Alldirectional compression
(hydrostatic pressure).
The expression 2.9 can be written in a short form if to use some evident rules
for operation with tensors which allow a constant to be taken away from bars.
Then
σ
ij
=
p 0 0
0 p 0
0 0 p
= p
1 0 0
0 1 0
0 0 1
















The remainder in bars is called the unit tensor or Kronecker Symbol, δ
ij
. For
the hydrostatic pressure
σ δ σ σ
ij ij ii ij
= p , i.e. = p; = 0 if i j − − ≠
For this stress tensor shear, the stresses are absent at any direction in space,
and it explains the term “hydrostatic” used for the situation shown in
Figure 2.8. The hydrostatic pressure (or simply  pressure) is evidently ex
pressed as
p =
+ +
3
=
I
3
11 22 33 1
− −
σ σ σ
[2.10]
The last definition is taken to be true for any stress state, even when σ σ
11 22
, ,
andσ
33
are not equal to eachother, and Eq 2.10 is considered as a general defini
tion of pressure, and the stress tensor, Eq 2.9, is called the spherical stress
tensor.
There is one intriguing question: whether the value I
1
/3 calculated according to
Eq 2.10, and called pressure, has the same physical meaning as pressure used in
any thermodynamic relationship? Certainly, it is true for hydrostatic pressure,
but this idea of arbitrary stress state needs a separate proof.
For plane shear stress state, whenσ σ
12 21
· , the principal stresses are equal to
σ σ σ σ σ
1 E 2 E 3
= ; = ; = 0 [2.11]
The same conclusion is correct for all other shear components of the stress ten
sor. It means that for this situation called simple shear, I
1
= 0, i.e., hydrostatic
A. Ya. Malkin 19
pressure does not exist. It proves that indeed shear stresses do not influence the
volume of a body but are able to change its shape only.
Nowwe can write down a general expression for any stress tensor with a sepa
rated hydrostatic component. In this approach, all shear stresses remain un
touched and each diagonal member of the tensor becomes equal to σ
ii
p − . This
part of the stress tensor (complete tensor minus hydrostatic component) is
called deviator or deviatoric part of the stress tensor. It is thought that this
part of the tensor is responsible for changes of shapes of a body (certainly at a
point).
The idea about splitting a stress tensor into spherical and deviatoric parts is
well illustrated by the example of uniaxial extension. Surely it is extension and
we have a right to expect that it leads to a volume change of a body. But is it all,
and is it equivalent to hydrostatic pressure?
Stress tensor for uniaxial extension is written as
σ
σ
ij
=
0 0
0 0 0
0 0 0








[2.12]
It reflects the situation in Figure 2.1, where all other forces except normal
force, F, are absent. There is no reason for the appearance of other stresses ex
cept for σ
11
, and that is why all components in the matrix 2.12 are zeros, except
for σ σ
11 E
= .
Let us separate this tensor into hydrostatic and deviatoric parts. In the case
under discussion, the matrix 2.12 shows that
σ σ σ σ
11 E 22 33
= ; = 0 and = 0
From Eq 2.10, it follows that p =  σ
E
/3. Now let us present the stress tensor
2.12 as a sumof hydrostatic pressure and remainder, where this “remainder” is
deviator or simply a difference between full stress tensor and hydrostatic pres
sure. Then the stress tensor for uniaxial extension can be written as:
20 Stresses
σ δ
σ
σ
σ
δ
ij ij
E
E
E
ij
= p +
2
3
0 0
0 
1
3
0
0 0 
1
3
= p −














+
3
2 0 0
0 1 0
0 0 1
E
σ








Any component of the full stress tensor, σ
ij
, is equal to the sumof components of
both addenda with the same indices; for example:
σ σ σ σ σ
11 E E E E
= p +
2
3
=
1
3
+
2
3
= − and σ σ σ σ
22 E E E
= p
1
3
=
1
3
1
3
= 0 − − −
One can see that the uniaxial extension is not equivalent to hydrostatic pres
sure (the sign is not essential in this discussion) as the former leads to appear
ance of a deviatoric component of the stress tensor. In particular, it means that
we can find such directions in a body where the shear stress exists (opposite to
hydrostatic pressure where the shear stresses are absent in principle) as men
tioned in discussion of Figure 2.6.
This interpretation of the uniaxial extension explains that in fact onedimen
sional tension creates not only negative pressure (“negative” means that
stresses are oriented from unit areas inside a body) but also different normal
stresses acting along all directions. This is a physical reason why in the uniaxial
tension all dimensions of a body change: a size increases along the direction of
extension but decreases in perpendicular (lateral) directions.
2.6 EQUILIBRIUM (BALANCE) EQUATIONS
The distribution of stresses throughout a body is described by equilibrium (or
balance) equations introduced by Navier,
2
Poisson,
3
and Cauchy.
4
In essence
they are one formof Newton’s Second Lawwritten for a continuumbecause they
state that the sum of all forces at a point is equal to the product of mass (of this
point) times acceleration.
A“point” inthe theoretical analysis is anelementary (infinitesimal) space with
sides oriented along the orthogonal coordinate axes (in Figure 2.9 this space is a
cube in the Cartesian coordinates). The idea of the analysis consists of a projec
A. Ya. Malkin 21
tion of all outer forces on faces of the
cube along three coordinate axes.
Let us consider a change of forces at
infinitesimal distance along an axis.
If there is no special situation with
jumps or breaks in force, we can
think that (for example) a force on
the lefthand face of the cube (Figure
2.9) equals to σ
22
, and on the parallel
ri ght hand f ace i t equal s to
σ σ σ ′ ∂ ∂
22 22 22 2 2
= + ( x )dx and the
sum of projections of forces is
( x )dx (dx dx )
22 2 2 1 3
∂ ∂ σ , where
(dx
1
dx
3
) is the surface area of the
face.
Writing the sumof projections of all
stress components parallel to x
2
axis
and dividing them by (dx
1
dx
2
dx
3
), we come to equilibrium (or balance equations
or equations of moment conservation). For all three coordinate axes, this ap
proach gives the system of equations:
∂
∂
∂
∂
∂
∂
σ σ σ
ρ
11
1
12
2
13
3
1 1
x
+
x
+
x
+ X = a
∂
∂
∂
∂
∂
∂
σ σ σ
ρ
12
1
22
2
23
3
2 2
x
+
x
+
x
+ X = a [2.13]
∂
∂
∂
∂
∂
∂
σ σ σ
ρ
13
1
23
2
33
3
3 3
x
+
x
+
x
+ X = a
where X(X
1
, X
2
, X
3
) is a vector of a body force per unit volume (dx
1
dx
2
dx
3
), a(a
1
, a
2
,
a
3
) is a vector of acceleration and ρ is the density.
For most rheological applications, it is reasonable to treat problems restricted
to static equilibrium, and hence a = 0. Besides, in many cases (but not always)
vector X equals zero. The existence of a body force is important, for example, in
22 Stresses
Figure 2.9. Stress difference at parallel sur
faces along the infinitesimal distance.
situations where the movement occurs because of the action of gravity: in sag
ging paints or sealants fromvertical or inclined surfaces, flowing of glaciers and
so on.
If we can omit two last members in the balance equations, it allows us to sim
plify the system, Eq 2.13, and in this case we can write it as follows:
∂
∂
∂
∂
∂
∂
σ σ σ
11
1
12
2
13
3
x
+
x
+
x
= 0
∂
∂
∂
∂
∂
∂
σ σ σ
12
1
22
2
23
3
x
+
x
+
x
= 0 [2.13a]
∂
∂
∂
∂
∂
∂
σ σ σ
13
1
23
2
33
3
x
+
x
+
x
= 0
Equilibrium can be considered in
respect to different coordinate sys
tems but not restricted to a Carte
si an system. The choi ce of
coordinates is only a question of con
venience in solving a concrete bound
ary problem. The choice of the
coordinate system depends, gener
ally speaking, on the shape and type
of symmetry of a geometrical space of
interest for the application. For ex
ample, if we deal with problems re
lated to round shells or tubes with
one axis of symmetry, the most con
venient coordinate system in this
case is cylindrical polar coordinates
with r, z, and θaxes.
Components of the stress tensor in these coordinates are shown in Figure 2.10.
The static balance equations (at a = 0) for the point (or infinitesimal volume ele
ment) shown in Figure 2.10 represent equilibriumin respect to r, z, andθ direc
tions and can be written as:
A. Ya. Malkin 23
Figure 2.10. Components of the stress tensor in
cylindrical polar coordinates.
∂
∂
∂
∂
∂
∂
σ σ σ
θ
σ −σ
θ θθ rr rz r rr
r
r
+
z
+
r
+
r
+ X = 0
∂
∂
∂
∂
∂
∂
σ σ
θ
σ σ
θ θθ θ θ
θ
r z r
r
+
r
+
z
+
2
r
+ X = 0 [2.14]
∂
∂
∂
∂
∂ ∂
∂
σ σ
θ
σ σ
θ zz z rz zz
z
r
+
r
+
r
+
z
+ X = 0
where X(X
r
, X
Θ
, X
z
) is a vector of a body force and its projections along the cylin
drical coordinates.
Some applied problems are symmetrical about the zaxis, so that all terms con
taining ∂ ∂θterms become zero and the shear stress σ
rΘ
as well. Besides, in
some cases, the cylindrical bodies can be very long and variations of stresses
along the axis of symmetry are absent (or can be taken as negligibly small). This
allows us to continue simplification of the balance equations, which in this case
reduce to
d
dr
+
r
+ X = 0
rr rr
r
σ σ σ −
ΘΘ
[2.15]
and all shear components of the stress tensor are absent.
2.7 EXAMPLES
It seems interesting and useful to present and discuss typical examples of
stress distributions in a body for some model situations.
2.7.1 A BAR LOADED BY THE CONSTANT FORCE (FIGURE 2.1)
This is a very popular scheme of loading, for example, when one suspends a
weight on a string or pulls a car frommud with a rope, or stretches a filament in
the technology of fiber spinning  all cases deal with a material under the action
of uniaxial extension. A similar scheme of loading, but with the opposite sign,
appears whena material or a part is compressedinone direction; for example, as
in pile loading or in building foundation.
24 Stresses
The stress distribution near the buttend of a bar depends on the manner of
counteracting the force. Far enough from the buttend (typically at a distance
larger thanthe characteristic transversal size of a bar), the distributionof forces
at the end becomes unessential for stress distribution throughout the bar and
normal stresses are calculated by the very simple and obvious relation 2.1. By
the abovediscussed method, all components of the stress tensor for different di
rections can be found.
2.7.2 A BAR STRETCHED BY ITS OWN WEIGHT (FIGURE 2.11)
It can be found in some engineering constructions
where parts are suspended at their upper end, or a plas
tic liquidlike stream, after leaving a nozzle, breaks by its
own weight at some distance from the nozzle.
Let a long bar (or a fiber) be suspended by its end. The
extensional (normal) stress along the bar appears as a re
sult of stretching by its own weight. According to the
equilibrium condition
σ ρ (x) = x [2.16]
The maximal normal stress is equal to σL, where L is
the length of the bar. It means that if the bar is very long,
the stress will exceed any acceptable limit and break the
bar.
2.7.3 SAGGING OF A FLEXIBLE BAR OR A FIBER (FIGURE 2.12)
Sagging of flexible engineering elements (bars, fi
bers and so on) is a rather typical situation in many
practical applications. The force provoking bar sag
ging can be caused not only by the own weight of the
bar but also by various outer factors (lying snow, push
of the wind, and so on). In all these cases, we deal with
distributed load, q, expressed as a force divided by the
length. The reasonable supposition says that the
height of flexure is much lower than the length of the
bar, or a span between supports, L, (in Figure 2.12
A. Ya. Malkin 25
Figure 2.11. A long
bar loaded by its
own weight.
Figure 2.12. A sagging
bar (fibre).
only a half of the bar is shown).
According to the equilibriumcondition (the sumof torques around the point of
suspension is equal to zero), we have:
Fy  qx
x
2
= 0
or
y =
qx
2F
2
The last formula shows that the shape of the loaded bar is parabolic. It is easy
to find the maximal sagging, H:
H=
qL
8F
2
[2.17]
Eq 2.17 allows us to find the necessary tension if we set acceptable flexure, and
vice versa. The normal stress in the bar is evidently equal to F divided by the
crosssection.
2.7.4 INTERNAL PRESSURE IN A THINWALLED CYLINDER (FIGURE 2.13)
This situation is of general meaning for all vessels working under internal
pressure, suchas chemical rectors, boilers, and different types of balloons, tubes
in tires, plastic films stretched during technological procedure of their shaping,
and so on.
26 Stresses
Figure 2.13. A thinwalled tube (cylinder) under internal pressure.
Let us try to calculate stresses in the wall of a cylinder loaded by internal pres
sure, p. We analyze the case when δ << R (the case named “thinwalled”). The
consideration of equilibrium across a radius gives the value of average stress
σ
ΘΘ
(or simply σ
Θ
):
σ δ
Θ
(2L ) = 2pRL
or
σ
δ
Θ
=
pR
[2.18]
(sinceδ <<R, we have a right not to distinguishouter and inner radii of the cylin
der).
Are other components of the stress tensor essen
tial? We can estimate the σ
rr
component (or sim
plyσ
r
). It is evident thatσ
r
= 0at the outer surface
and σ
r
= p at the inner surface of the cylinder. It
means that σ
r
is of the order of pR. Because we as
sume that R/δ >> 1, it means that σ
r
is negligible
in comparison withσ
Θ
. The σ
zz
and all shear com
ponents are absent in the case of thinwalled
items, as usual.
The situation changes if we assume that such a
vessel must be closed by a lid (Figure 2.14). It is
rather evident that there is a force acting on the
surface of a ring joining the lid and the cylinder. This force resists the action of
internal pressure and it leads to the following equation for the stress component
σ
zz
(or simply σ
z
):
p R = 2 R
2
z
π π δσ
Then
σ
δ
z
=
pR
2
[2.19]
A. Ya. Malkin 27
Figure 2.14. Stresses in a
spherical lid of a vessel.
Now, we come to the conclusionthat there
is a twodimensional (or plane) stress state
in the wall of the cylinder as shown in Fig
ure 2.15 for a “unit” (or infinitesimal)
square. Both stresses σ σ
Θ
and
z
are princi
pal as shear stresses are absent. The third
principal stressσ σ σ
r z
<< and
Θ
and can be
taken equal zero.
2.7.5 HEMISPHERICAL MEMBRANE UNDER ITS OWN
WEIGHT (FIGURE 2.16)
We face this type of loading in many engi
neering constructions, especially when a
spherical roof covers a large area of a sta
dium or a storehouse. This problem (simi
lar to that discussed above) relates to
stress fields in shells or plates (mem
branes). The shape of a membrane in this
case is defined as
r = Rsinα
Let the density of the membrane beρ. The thickness of a hemisphere is uniform
and equal toδ (δ is taken as much smaller than R). Theory gives the following ex
pression for the normal stress acting along the surface of the hemisphere:
σ ρ = gR
[1 (r / R) ] 1
(r / R)
2
2
1
2
−
[2.20]
where g is the gravitation constant.
At the support ring (r = R) stresses must balance the total weight of the hemi
sphere and that is why
σ = gR −
is the maximal value of the principal stress, σ.
28 Stresses
Figure 2.15. Plane stress state in a
wall of a cylinder.
Figure 2.16. Hemispherical cup
loaded by its own weight.
2.7.6 TORSION OF A THINWALLED CYLINDER (FIGURE 2.17)
This is a model situation for many ap
plications. For example, it is a scheme of
a typical rotational viscometer widely
used for measuring rheological proper
ties of different substances. Then this
scheme reflects such a classical engi
neering situation as joining tubes with
fitting.
Let the wall of a cylinder, δ, be much
smaller than its radius, R, (as in Exam
ple (iv)). The cylinder is loaded by the
torque, M. In this case, it is reasonable
to assume that there is an average (constant) shear stress σ σ σ = =
z z Θ Θ
over the
wall section.
From the condition of static equilibrium, one can derive:
M= S(R+ 2) δ σ
whereS 2 (R+ 2) ≈ π δ δ is the area of a ring (section of the cylinder). As a result,
the shear stress is given as:
σ
π δ δ
=
2M
(2R+ )
2
[2.21]
In the case under discussion, a torque can be produced by relative turning, ro
tating or twisting of cylinders (inner or outer with no difference for the result).
Eq 2.21 is applicable in this case if the condition δ << R is fulfilled.
2.7.7 TORSION OF A CONE OVER A PLATE (FIGURE 2.18)
It is practical to analyze this situation because it applies to a socalled
“coneandplate” viscometer, used in the plastic and rubber industries, as well
as to scientific investigations.
We analyze a case whenthe angleα betweensurfaces is small. This situationis
interesting (and rather simple) because at very low values of the angle α the
A. Ya. Malkin 29
Figure 2.17. Torsion (shear) of a long
thinwall cylinder.
shear stress, σ, is practically constant
throughout the volume of a material be
tween the cone and the plate. Balance of
forces gives the following expression for σ:
σ θ = C sin
2
[2.22]
where Cis a constant andthe angleθ is taken
from a vertical axis. Values of θ throughout
the gap, between the cone and plate, are very
close to π/2, then sin
2
θ ≈1and σ = const.
Integrating along the radius R gives the fi
nal relationshipfor torque andshear stress:
σ
π
=
3M
2 R
3
[2.23]
2.7.8 STRESSES IN A MEDIA MOVING ALONG A CYLINDER (FIGURE 2.19)
This is the simplest and per
haps the most important hydro
dynami c pattern havi ng
general meaning for transpor
tation of water, oil products,
raw materials in the food and
pharmaceutical industries, and
in numerous other cases.
If to write the balance equa
tion for the element of the
length, dz, loaded by pressure
gradient, dp/dz, we come to the
following relationship:
σ π π (2 r)dz= r dp
2
or
30 Stresses
Figure 2.18. Rotation of a cone over
a plate.
Figure 2.19. Movement of a mediumalong a cylinder.
σ =
r
2
dp
dz
[2.24]
where σ σ σ = =
zr rz
is the shear stress, and r is a current radius, i.e., distance
from the axis of the cylinder.
The last equation shows that the shear stress at the wall, σ
w
, (maximal shear
stress) is calculated as
σ
w
=
R
2
dp
dz
[2.25]
and the stress distribution along the radius of the cylinder (or the tube or capil
lary) is linear:
σ σ =
r
R
w
[2.26]
The diagram in Figure 2.19 says nothing about other
components of the stress tensor; though normal (diago
nal) stresses definitely exist (at least pressure, p, cre
ates alldirection compression), only pressure gradient
(not pressure itself) influences the shear stresses.
2.7.9 STRESSES AROUND A CIRCULAR HOLE IN A SHEET (FIGURE 2.20)
Since practically all parts of engineering and every
day applications have holes of different sizes and
shapes, it is very important to knowhowthese holes in
fluence performance characteristics of a part. Intechni
cal language, this influence is associated with stress
fields appearing in the neighborhood of a hole. A round
(circular) hole is the simplest example of possible
shapes of holes, thoughholes canhave different shapes.
If a sheet having a circular hole is stretched by a uni
formload, p, stress is created around the hole. Fromthe
equation of equilibrium, it is possible to find (we omit
the details) that the distribution of stresses exists
A. Ya. Malkin 31
Figure 2.20. A circu
lar hole weakening a
flat sheet.
around the hole. All components of the stress tensor depend on relative radius
(r
0
/r) (r
0
is the radius of the hole and r is a distance from the center of the hole,
r>r
0
) and the angle, θ, between the axis of the load action and an arbitrary direc
tion.
Calculations show that stresses decrease very rapidly away from the edge of
the hole (in fact they are decreased as a function of (r
0
/r)
2
).
Most important is the situation at the hole boundary, where the stresses are
maximal and equal to:
σ θ
ΘΘ
· − p( cos ) 1 [2.27]
(at r
0
/r = 1 other components of the stress tensor are absent).
The limiting values of σ σ
Θ ΘΘ
= are:
σ θ π θ π = 3p at = 2and = 3 2
σ θ θ π = p at = and = −
This phenomenon is called stress concentration (due to cracks) and larger
stresses (incomparisonwiththe average value) lead to weakening inbodies con
taining holes.
Inthe case showninFigure 2.20, the side points, X, of the hole are the most vul
nerable (in respect of possible fracture) because the stress is three times higher
than the average stress, p.
If extensionchanges to compression(applied stress is equal to p), the maximal
tension occurs at the points Y, and in this situation these points become the ar
eas of likely failure.
2.8 CONCLUDING REMARKS
Stress is the dynamic characteristic at a point and is defined as the relative
force or the force related to the unit area. Stress values depend on direction of
the applied force and the orientation of a surface for which we wish to find forces
acting at this surface inside a body. That is why stress is a physical object of ten
sor nature. Stresses can be normal (perpendicular) and shear (tangential) to
the surface where they act.
It is always possible to calculate components of the stress tensor for any direc
tion and to find principal directions and principal normal stresses; the latter
32 Stresses
are extremal and shear stresses are absent at those directions.
There are three special combinations of any arbitrary stress tensor which do
not depend on choice of axes orientation in space. These combinations are called
invariants.
The stress tensor can be divided into two parts, one of which (sonamed spher
ical) is responsible for volume and the other (called deviator) for shape (or
form) changes of a body (at a point).
Calculating stresses through a body is realized by solving differential equa
tions with appropriate boundary conditions. These equations represent the law
of equilibrium (or balance) of all forces applied at a point.
Concrete examples of calculations for some simple geometrical forms show
that different situations are possible: uniform and distributed, onedimen
sional, plane, or volume stress fields.
The examples discussed above are typical due to simple (model) geometrical
forms of bodies under analysis. They allowed us to find stress fields regardless of
the particular properties of the material. But inmany other cases, it is necessary
to analyze not only stress but deformation fields jointly. It leads to the necessity
to take into account relationships between stresses and deformations, i.e., rheo
logical properties of matter.
2.9 REFERENCES
1. A. L. Cauchy, De la pression ou tension dans un corps solide, Ex. de Math., 1827.
2. C. L. Navier, Mémoire sur les lois de l’équilibre et du mouvement des corps
solides élastique, Mém. Acad. Sci. Inst. France, 1827.
3. S. Poisson, Mémoire sur l’équilibre et le mouvement des corps élastiques, Mém. Acad.
Sci. Inst. France, 1829.
4. A. L. Cauchy, Sur les équations differentielles d’équilibrium ou de mouvement pour le
points matériels, Ex. de Math., 1829.
A. Ya. Malkin 33
3
DEFORMATION
AND DEFORMATION RATE
3.1 DISPLACEMENTS AND DEFORMATIONS
The result of action of outer
forces can be either movement of
a body in space or change of its
shape. Here, we are interestedin
describing the changes occur
ring inside a body. The change of
a shape of a body is essentially
the change of distances between
different points on its surface.
Thus, change of shape can only
occur if there are changes of dis
tances between different sites
inside a material, and this phe
nomenon is called deforma
tion.
The change of distances be
tween points inside a body is
transmitted to the neighborhood
of a point which can be moni
A. Ya. Malkin 35
Figure 3.1. Displacement of two points in a body and
appearance of deformation.
tored by following the change of very small (infinitesimally small) distances be
tween two points.
Let the distance betweentwo points Aand Bina material be ds (Figure 3.1). As
a result of some outer action, they both move and their new positions become A′
and B′, and the distance betweenthemnowis ds′. The absolute value of (ds’ − ds)
is not important, because the initial length ds might be quite arbitrary, only rel
ative change of the distance between two sites, determined as
ε =
ds ds
ds
′ −
[3.1]
The definition 3.1 is not tied to any coordinate system, meaning that ε is a sca
lar. It can be expressed through components of tensor of deformation (or
strain), ε
ij
. The position of a site in a body is characterized by its radiusvector,
r, and, because we have two sites, it is necessary to introduce two vectors: r
1
for
the point A and r
2
for the point B. The quantitative determination of deforma
tioncanbe accomplished by following the relative displacement of two vectors,
expressed as (dr
1
 dr
2
)/dr
1
. If we assume that a body after deformation remains
intact (between sites A and B), the distance between points A’ and B’ is still in
finitesimal.
The difference (dr
1
 dr
2
) is a displacement, u. As a difference of two vectors, it is
also a vector which can be expressed by its three projections: u(u
1
, u
2
, u
3
). Rela
tive displacement is characterized not only by its length but also by its orienta
tion in space. Since two vectors, u and x(x
1
, x
2
, x
3
), describe relative
displacement, the latter is of tensorial nature. Indeed, deformation and relative
displacement are tensors and components of these tensors can be calculated as
derivatives du/dx. It is also pertinent that there are nine such values (three pro
jections of vector u and three of vector x), as could be expected for a tensor. The
values of all derivatives are dimensionless and they are expressed in absolute
numbers or percents.
Accurate calculations of the components of the deformation tensor give the fol
lowing expression:
ε
ij
i
j
j
i
1
i
1
j
2
i
=
1
2
u
x
+
u
x
+
1
2
u
x
u
x
+
u
x
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂u
x
+
u
x
u
x
2
j
3
i
3
j
∂
∂
∂
∂
∂
[3.2]
36 Deformation and deformation rate
The complete expression for ε
ij
consists of linear (first parentheses) and qua
dratic (second parentheses) terms. In many cases, derivatives in this formula
are very small (<< 1) and their pair products, which enter into the second
righthand member in Eq 3.2, are negligibly smaller than derivatives. Hence
they can be omitted, and thus only the two first members (first parentheses) of
the equation are essential. It is only true if deformations are small, and that is
why the tensor consisting only of first derivatives is called an infinitesimal de
formation (or strain) tensor. This tensor, d
ij
, is as follows:
d
u
x
1
2
u
x
u
x
1
2
u
x
u
x
ij
1
1
1
2
2
1
1
3
3
1
=
+
+
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
+
+
1
2
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
u
x
u
x
u
x
1
2
u
x
u
x
2
1
1
2
2
2
2
3
3
2
+
+
1
2
u
x
u
x
1
2
u
x
u
x
3
1
1
3
3
1
1
3
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
u
x
3
3
[3.3]
where the first line represents the projections of deformation along the x
1
axis,
and so on.
In this Section we shall discuss only small deformations. The large deforma
tions (if the first derivatives in Eq 3.2 are not small) will be considered in a sepa
rate Section below.
Relative displacement is definitely the cause of deformations inside a body.
Are both displacement and deformation identical in this case? In order to an
swer this question, let us calculate the relative displacement which is, by defini
tion, a gradient of u:
g = grad u
The result can be presented in the form of a matrix:
A. Ya. Malkin 37
g =
u
x
u
x
u
x
u
x
u
x
u
x
u
x
u
ij
1
1
1
2
1
3
2
1
2
2
2
3
3
1
3
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂
∂x
u
x
2
3
3
∂
∂
[3.4]
where the first line includes derivatives of the u
1
component of displacement
along three coordinate axis, the second line is the same for the u
2
component,
and the third, for the u
3
component of the vector u.
It is quite evident that the tensors d
ij
and g
ij
are not equivalent. The difference
between them becomes clear if we decompose components of the tensor g
ij
into
two parts in the following manner:
g =
u
x
=
1
2
u
x
+
u
x
+
1
2
u
x
u
x
ij
i
j
i
j
j
i
i
j
j
i
∂
∂
∂
∂
∂
∂
∂
∂
−
∂
∂
[3.5]
The first, socalled symmetrical, part of the tensor g
ij
coincides with the defor
mation tensor d
ij
, but
g
ij
≠ d
ij
Then, we need to understand the physical meaning of this difference or the
meaning of the second, socalled antisymmetrical, part of the displacement
tensor. Figure 3.2 helps to explainthe concept. Let us followthe deformationof a
body element drawnas a rectangle. Two displacements, u
2
and u
1
, having gradi
ents du
2
/dx
1
and du
1
/dx
2
, may occur as shown in the central part of Figure 3.2.
Now, let us superimpose these two displacements, as shown on the right dia
gram. It is evident that the summationof du
2
/dx
1
anddu
1
/dx
2
does not leadto de
formation but to rotation of the body element. It means that the second term in
Eq 3.5 represents rotation,but not deformation. It can be written in the follow
ing form:
g
ij
= d
ij
+ θ
ij
[3.6]
38 Deformation and deformation rate
where θ
ij
consists of differences of the structure
θ
ij
i
j
j
i
=
1
2
u
x
u
x
∂
∂
−
∂
∂
[3.7]
and describes the rotations (turns) of infinitesimal volumes inside a body. Thus
displacement at any point of a body is a sum of deformation and rotation.
3.2 DEFORMATION RATE
If velocity (as a vector), at any point of a body, is the same, it means that a body
moves as a whole and no deformationtakes place. The deformationappears only
as a consequence of velocity gradient at “a point”, which means that two neigh
boring sites (the distance between them being infinitesimally small) move with
different velocities. If velocity is v(a vector value), its gradient is calculatedas
A. Ya. Malkin 39
Figure 3.2. Superposition of two shear deformations leading to rotation.
a
ij
= dv/dr [3.8]
where space coordinates are described by radiusvector, r. Thus a
ij
is a tensor de
termined by two vectors (v and r). The velocity is the rate of displacement,
i.e., v = du/dt. The relationship between gradient of velocity and gradient of dis
placement can be found from the equation:
a =
d
d
=
d
d
d
dt
=
d
d dt
=
d
dt
d
d
=
dg
d
ij
2
ij
v
r r
u u
r
u
r
t
In the previous section, it was established that the whole gradient of displace
ment is not controlling deformation, only its symmetric part. The same is true
for the deformation rate. The reasoning is the same as above. Differentiation in
respect to scalar  time, d/dt,  adds nothing new to the result. By decomposing
tensor a
ij
into symmetrical and antisymmetrical components,
a =
1
2
v
x
+
v
x
+
1
2
v
x
v
x
ij
i
j
j
i
i
j
j
i
∂
∂
∂
∂
∂
∂
−
∂
∂
[3.9]
one obtains
a
ij
= D
ij
+ w
ij
[3.10]
where D
ij
is the rate of deformation tensor, and w
ij
is the socalled vorticity
tensor. As in the previous case, the rate of deformation tensor characterizes lo
cal changes of shape. The deformation is related to the first termin Eq 3.9, while
the vorticity tensor describes the rate of rotationof local elements of a body with
out their deformation.
The difference betweentensors a
ij
and D
ij
(similar to g
ij
and d
ij
) canbe easily illus
trated by a simple example. Let us analyze the rotation of a solid (nondeform
able) body around some axes. The velocity, v, at a point located at the distance, r,
fromthe axes is equal toωr, whereωis the constant angular velocity. Thus v =ωr,
and the gradient of velocity, grad v = dv/dr, is evidently equal toω. It means that
in rotation of a solid body the gradient of velocity does exist but there is no defor
mation (because the body was assumed to be nondeformable).
40 Deformation and deformation rate
3.3 LARGE DEFORMATIONS
The difference between small and large deformations depends on the value of
derivatives in Eq 3.2. If all derivatives are much smaller than 1, the quadratic
terms can be neglected, i.e., products of derivatives (in parentheses), and the
tensor d
ij
is used instead of ε
ij
.
Inthe discussionof a concept of large deformations, it is always assumedthat a
reference state for deformation can be established. In this sense, flow of a liquid
may not be considered as deformation because all states are equivalent. Liquid
does not have initial (or reference) state. That is why only materials having
memory of their initial state are important here.
Having such an approach, it is very easy to illustrate the essential difference
between small and large deformations, using the model from Figure 3.3. Let a
bar of the length l
o
be stretched by ∆l. The simple question is: what is the defor
mation in this case?
In the first case, let l
o
= 1
and ∆l = 0.1. The socalled
engineering measure of
def ormati on equal s
ε *= l l = 0.1 ∆ (or 10%),
and it is expressed as
ε
11 1 1
= du dx . The rea
soning becomes much
more complicated if ∆l is
comparable with l, for ex
ample, if ∆l = 1. Certainly
in this case we also can
use an engineering mea
sure of deformation as a
characteristic of change of
specimen length, and it is
equal to 1 (or 100%). But
this approach to the definition of deformation contains an inherent contradic
tion. Let us compare two situations, drawn in Figure 3.3: In the first case (case
I), the increase in the length occurs in two steps: initially by ∆l
1
and then ∆l
2
.
Then the deformation in the first step is ε
1 1 o
*= l l ∆ and ε
2 2 1
*= l l ∆ in the
A. Ya. Malkin 41
Figure 3.3. Two ways of realization large deformation of uni
axial extension.
second step, because initial length of a sample in the second step is l
1
. Then the
complete deformation is the sum of both
ε ε ε
I 1 2
1
o
2
1
o 1 2 1
2
o 1
*= *+ *=
l
l
+
l
l
=
l ( l + l ) + l
l l
∆ ∆ ∆ ∆ ∆
In the second case (case II), the increase of the length is achieved in one step.
This increase is equal to (l
1
+ l
2
) and the deformation ε
II
* is calculated as
ε
II
1 2
o
o 1 2 1
2
1 2
o 1
*=
l + l
l
=
l ( l + l ) + l + l l
l l
∆ ∆ ∆ ∆ ∆ ∆ ∆
The ε ε
I II
* * ≠ contradicts the physical meaning of the experiment’s interpre
tation because the final result is not the same in both cases; the sample does not
“know” which way it was brought to the final state, whereas calculations showa
difference. This appears only as a result of large deformations, because if defor
mations are small, the quadratic terms in formulas for ε ε
I II
*and *are negligi
ble in comparison to the linear terms, and in this approximation (which is quite
reasonable if ∆l
1
and ∆l
2
<< l
o
) both measures of deformation become identical.
From the above, it becomes apparent that there is a need to introduce such
measure of deformation which does not depend on the order of operations. Such
measure is called a Hencky measure,
1
ε
H
, defined by:
ε
H
= ln( l l) ∆ [3.11]
Large deformations analyzed by this measure obey the law of additivity. It is
easy to note that in the example discussed above
ε ε
I
H
II
H
=
i.e., the result does not depend on the history of deformation, as required.
Inrheological literature, some other values are used as a measure of deforma
tions. In fact, any function of deformation can be treated as a measure of defor
mation. One of the most widely used is the socalled Cauchy  Green tensor of
deformation, C
ij
. It is directly related to the concept of large deformations ex
42 Deformation and deformation rate
pressed by Eq 3.2, and the CauchyGreen tensor is determined as:
C = + 2
ij ij ij
δ ε [3.12]
where δ
ij
is the unit tensor (or Kronecker delta).
The Cauchy  Green tensor characterizes change of the distance between two
arbitrary “particles” in a “point”: here again we speak about a point, not as a
mathematical idea, but as a physical object which contains many “particles”.
Another tensor of large deformations is frequently used. This is the tensor in
verse (or reciprocal) to the Cauchy  Green tensor, C
ij
, named the Finger ten
sor, C
ij
1
. According to the definition, the relationship between both is
C C =
ij ij
1
ij
δ
Introducing different measures of deformations does not exclude the main
question regarding the initial state  point of reference of the deformed state.
The value of this question has been already demonstrated by the example of
large deformations in uniaxial extensions. For static states this problem can be
solved by introducing the Hencky measure of deformations. But the same prob
lem appears and becomes more pertinent for a continuously moving medium
where the position of deformed elements of a body is changing in time and we
want to describe the process or the rate of deformation.
Asimilar situationhas importance inclassical hydrodynamics where transfor
mation is followed (for example, temperature effect or chemical reaction) in
moving media. Insucha case, the problemis solved by using a socalled material
or substantial derivative, D/Dt, which can be written for any arbitrary vari
able, Y, as
DY
Dt
=
Y
t
+
v Y
x
k
k
∂
∂
∂
∂
∑
[3.13]
The mainnewapproachwhichappears inthe theory of large deformations con
cerns the importance of knowing the rate of deformation not only in a fixed coor
dinate system but in moving one, as well. It means that the behavior of a
material in moving sites must be described because changes occur not at a point
of a space but in a traveling element of a material which deforms along its re
A. Ya. Malkin 43
placement. This concept is called the principle of material objectivity and it
states that all physical phenomena, certainly including laws of deformation,
must not depend on a coordinate system used for their mathematical formula
tion.
As a result of large deformations, material elements can travel far away from
their initial position, and that is why it is important to apply proper rules of
transition from the reference state. Similar to our discussion of large uniaxial
extension, it is also important here that the choice of different reference states
must not leadto anambiguous estimationof deformation. Anobserver who mea
sures properties of a material is always positioned in fixed (unmovable) coordi
nate system. Hence the general approach consists of formulating ideas
concerning possible rheological behavior of a material for a moving (and deform
ing) element of a medium, recalculating them into a fixed coordinate system,
and then comparing the results with an experiment.
This is completely true for the rate of deformation. There are different mathe
matical ways to realize the idea of transformation of the rate of deformation ten
sor into a fixed coordinate system and, depending on the choice, various special
forms of time derivatives, generalized by Eq 3.13. Moreover, in some theoretical
studies, there is a necessity to introduce kinematic tensors of a higher order
hich are determined as time derivatives of the CauchyGreen or Finger ten 
sors. They are used if it is assumed that rheological behavior of a material de
pends, not on the rate of deformation only, but on higher derivatives of
deformation, as well. In Chapter 7, devoted to properties of viscoelastic materi
als, their behavior is modeled by equations containing a sum of nth order time
derivatives of deformation (socalled rheological equations of a differential
type). If deformation is large, one needs to use measures of large deformations
and calculate their time derivatives.
In the case of the substantial time derivative, D/Dt, the physical meaning of
this operation requires us to calculate derivatives for a moving medium which
follow time changes in a material point changing its initial position. This prob
lemin the theory of large deformations is solved by introducing time derivatives
of a different type. The most popular are the Rivlin  Eriksen, A
n
(t), and White 
Metzner, B
n
(t), tensors of the nth order.
2
They are determined as
44 Deformation and deformation rate
A (t) =
D C (t)
Dt
n
n
ij
n
and
B (t) =
D C (t)
Dt
n
n
ij
1
n
−
where C
ij
and C
ij
1
are the CauchyGreen and Finger tensors, respectively.
SaintVenant
3
was the first who realized the necessity to consider the concept
of large (finite) deformations. Later ideas of the theory of large deformations
were discussed and developed by Finger,
4
Zaremba,
5
Cosserat,
6
and Jaumann.
7
Fundamental works were also contributed by Biot.
8
More recently, Rivlin
9
dis
cussed studies on large deformations in numerous publications. A complete
treatise on modern theories of large deformations of solids is included in book by
Green and Adkins,
10
and for liquids, by Lodge.
11
The use of various measures of
large deformations and different types of their time derivatives allows one to ar
rive at qualitative predictions concerning possible effects in rheological behav
ior of a material, but it is the task of an experiment to find a model which can
adequately describe physical phenomena observedfor different real materials.
3.4 PRINCIPAL VALUES AND INVARIANTS OF THE DEFORMATION TENSORS
The principal deformations (strains) are calculated in the same way as
principal stress. For the infinitesimal deformation tensor, the principal defor
mations, d
1
, d
2
, andd
3
, are extensions along three orthogonal directions. It canbe
illustrated by a very spectacular picture of deformations in the vicinity of some
point. For this aim, let us represent an infinitely small volume in a body as a
sphere (Figure 3.4) with a center positioned at a point Aand radius of the sphere
dr (infinitesimal small length). The coordinates of the central point A are x
1
, x
2
,
and x
3
. As a result of movements and displacements, the following changes have
taken place in a body: the point Ahas moved to a newposition A*, the directions
of the radii AB, AC, and AD have changed to the directions A*B*, A*C*, and
A*D*, respectively. And the sphere itself has transformed into an ellipsoid with
semiaxes of lengths (1 + d
1
)dr, (1 + d
2
)dr, and (1 + d
3
)dr, respectively.
A. Ya. Malkin 45
The deformations characterize the change of the shape of a volume element of
a body — transition from a sphere to an ellipsoid. Besides they determine the
relative change of the volume, ε
v
, which can be written as follows:
ε
v
ell sph
sph
=
V V
V
−
[3.14]
Simple calculation shows that
ε
v
= (1 + d
1
)(1 + d
2
)(1 + d
3
)  1 [3.15]
It is very easy to show that ε
v
is expressed through invariants of the deforma
tion tensor because change of volume must not be associated with the choice of
the coordinate system, and the invariants do not depend on the coordinate axes.
If deformations are small and it is possible to neglect quadratic terms incompar
ison with linear terms, the Eq 3.15 gives a particularly evident result:
ε
v
= d
1
+ d
2
+ d
3
[3.16]
i.e., volumetric changes are equal to the first (linear) invariant of the tensor of in
finitesimal deformations and that is the physical meaning of the latter.
46 Deformation and deformation rate
Figure 3.4. Transformation of a sphere into an ellipsoid as a consequence of three principal defor
mations along their axes.
The volumetric changes indeformationcanalso be represented throughexten
sion ratios. For this purpose, let us (conditionally) cut out a small rectangular
parallel pipe, at a some site in a body, oriented along the principal axes. Let the
lengthof its edges be a, b andc before deformation, andbecome a*, b*, andc* as a
result of deformation. Then the extension ratios are:
λ λ λ
1 2 3
= a * a; = b* b; = c * c
and the volume change is calculated as
∆V + V
V
=
a * b*c *
abc
=
1 2 3
λ λ λ
The last formula allows one to state a very simple rule of constancy of volume
in deformations of any type:
λ λ λ
1 2 3
1 = [3.17]
Like any other tensor, the deformation tensor, d
ij
, can be decomposed into
spherical and deviatoric parts. Considering that the first invariant is the vol
ume change, we can write:
d =
3
+ d
ij
v
ij
ij
(dev)
ε
δ
where the second member in the righthand part of the equation is a deviatoric
part, d
ij
(dev)
, of the d
ij
tensor which describes shape transformation occurring
without changes in volume.
3.5 UNIAXIAL ELONGATION. POISSON RATIO
Let a bar of sufficient length to be stretched and increase its length by ∆l/l
0
or
the extension ratio, λ, be (∆l + l
0
) /l
0
. If (du
1
/dx
1
) = λ  1, one can write
ε λ λ λ
11
1
1
1
1
2
2 2
=
du
dx
+
1
2
du
dx
= ( 1) +
1
2
( 1) =
1
2
(
− − −1) [3.18]
A. Ya. Malkin 47
Additional to being stretched in the axial direction, the bar undergoes changes
in the lateral direction. The relation between relative changes of dimensions in
the lateral and axial directions cannot be established on the basis of a purely
geometrical picture of deformations because this relation is an inherent, inde
pendent property of a material. The quantitative characteristics of this property
is the ratio of relative lateral contraction to the relative longitudinal extension
and this special property of a material is called the Poisson ratio.
For simplicity, let the bar have a round crosssection with the radius, r
o
, and
the length, l
o
. If its elongation is ∆l, and, as a result of stretching, radius is de
creased by ∆r, then, by definition, the Poisson ratio, µ, is:
µ =
r r
l l
o
o
∆
∆
[3.19]
It is now easy to calculate the volume change, resulting from uniaxial stretch
ing. The relative change of volume ∆V/V is
∆
∆ ∆
V V =
(r + r) (l + l) r l
r l
o
2
o o
2
o
o
2
o
−
[3.20]
If ∆l << l
o
and consequently ∆r << r
o
(small deformations), the last formula
gives
∆V V = (1 2 ) − µ [3.21]
Poisson ratio is a measure of volume changes during small deformations. From
Eq 3.21, one can see that deformations occur without volume changes when and
if µ = 0.5. For real solid materials, µ < 0.5, meaning that their elongation is ac
companied by increase in volume. Only for some rubbers µ = 0.5.
It is interesting to use the general method of decomposing the deformationten
sor, d
ij
, into spherical and deviatoric terms for uniaxial extension. If λ << 1, and
deformationis equal toε, the deformationtensor for suchcase canbe writtenas:
48 Deformation and deformation rate
d =
0 0
0  0
0 0 
=
1 2
3
+
1+
3
2 0 0
0 1 0
0 0
ij ij
ε
µε
µε
µ
εδ
µ
ε
−
1
The structure of this sumis very similar to the structure of the stress tensor de
composition into two parts (compare with the analogous procedure in
Chapter 2). Asimilar approachwill also be takeninthe next Chapter for the dis
cussion of elasticity theory.
More precise analysis of Eq 3.20 shows, however, that for large deformations
Eq 3.2 is not valid, and the rule of µ=0.5 as the conditionfor maintaining the con
stant volume at stretching has no general meaning. Indeed, preserving the for
mal definition 3.19 for the Poisson ratio, according to Eq 3.20, we have for
∆V/V=0:
1 2 (1+ ) + (1+ ) = 0
2
− µ ε µ ε ε [3.22]
If ε << 1, Eq 3.22 is converted to an ordinary condition such that µ = 0.5, but in
the more general case it is not true. For example, let the bar be stretched by 9
times (it is quite possible for rubber ribbons or melted fibers). It means that
∆l l
o
= 8 and the volume can remain unchanged if the final radius becomes
equal to 1/3 of its initial value. Then ∆r / r
o
= 2 3. In this case according to Eq
3.22, and formal definition 3.19, µ = 1 12. This example shows that adaptation
of infinitesimal deformation mechanics (µ = 0.5 as a necessary condition for con
stant volume at extension) to the range of large deformations must not be done
in a straightforward manner.
3.6 SIMPLE SHEAR AND PURE SHEAR
Simple shear is a very important type of deformation because movement of
all fluids and liquidlike materials is based on the principle of sliding of neigh
boring layers relative to each other. The schemes of simple shear for an element
of a body in the case of small deformations, and in the general case of arbitrary
deformation, are showninFigure 3.5 a andb, respectively. Along the directionof
shear marked by an arrow, a displacement, u
1
, takes place. Its gradient,
du
1
dx
2
, is determined by the slope which will be denoted as γ:
A. Ya. Malkin 49
γ = tanα = du
1
dx
2
Since the length of linear elements, which were oriented before deformation in
the x
2
direction, is changed in shear, one more displacement component, u
2
, ap
pears. It is related to the change in the length of the segment OA, which after
displacement now becomes OA*:
( )
OA * OA
OA
= 1+ 1
2
1
2 −
− γ [3.23]
The value of γ = du
1
/dx
2
for simple shear determines all components of the ten
sor at large deformations. According to the deformation of theε
ij
tensor, its com
ponents are:
ε ε γ
12 21
= =
1
2
ε γ
22
2
=
1
2
This tensor is graphically illus
trated in Figure 3.5 b in which the
components of the tensor, ε
ij
, are
marked by arrows (factor 1/2 is omit
ted in drawing this Figure). The ap
pearance of a diagonal component in
the deformation tensor in a simple
shear is a direct consequence of large
deformations because ε
22
is propor
tional to γ
2
and its value becomes
negligible if γ <<1. This phenomenon
is known as the Poynting effect,
observed in twisting of wires: their
length slightly changes in this case.
Twisting is an example of shear de
formation, and the observed change
of the length in the axis direction is
50 Deformation and deformation rate
Figure 3.5. Small (a) and large (b) deformations
in simple shear.
restricted to ε
22
component of the deformation tensor.
Let us now discuss some models of simple shear which are often used in rheo
logical literature and are illustrative for the tensorial nature of the deformation
tensor.
The angle, β, between the direction of shear, x
1
, and the orientation of the prin
cipal axis is calculated as
β γ =
1
2
atan( 2) [3.24]
The main components of the deformation tensor may be written as follows:
γ λ γ λ γ λ
1 1
1
2 2
2
3 3
2
=
1
2
( 1); =
1
2
( 1); =
1
2
( 1) − − − [3.25]
where λ λ λ
1 2 3
, ,and are principal elongations (or extension ratios in the direc
tions of principal axes). These values are related to the angleβin Eq 3.24, and to
the plane deformation state (as in Figure 3.5); they are as follows:
γ β γ β γ
1 2 3
= cot , = tan , and = 1
A result obtained from the last set of formulas for λ
i
indicates that in simple
shear no volume change occurs because γ γ γ
1 2 3
1 = in accordance with Eq 3.17.
Components of the Cauchy  Green tensor in shear are important for theoreti
cal discussion concerning rheological models of elastic liquids. Calculations give
the following expression for C
ij
:
C =
1 0
1+ 0
0 0 1
ij
2
γ
γ γ
In a simple shear, not only the lengths of linear elements change (e.g., along
the principal directions), but rotation of the elements of a body also takes place.
This effect is illustrated inFigure 3.5, where the angle of turn(rotation), θ, of the
diagonal from OC to OC* position, is shown.
A. Ya. Malkin 51
Shear deformation, AA*, inthis Figure, is due to displacement, andα is its gra
dient. Any gradient of displacement consists of deformation and rotation, which
ingeneral formis expressed by Eq 3.5. For small displacement, the angle of rota
tion, θ α = 2, must be used, unlike for large deformations, where the general Eq
3.5 is applicable.
It is possible to find such shear conditions where no rotation occurs. This case,
called pure shear, is based on definition of the ω
ij
from Eq 3.7. It is seen that
ω
ij
= 0 if all differences of the displacement gradient equal zero. For the simple
shear, this condition has following form: du
1
/dx
2
= du
2
/dx
1
.
Geometrical image of a pure shear is drawn in Figure 3.6. In pure shear the di
agonal AB of the small square (at some point) moves, due to deformation, into
newposition A*B*, parallel to its initial position, and the diagonal OMdoes not
change its position at all, being only
extended to OM*; therefore, no ele
ment of the body undergoes rotation.
Figure 3.6 can be obtained in a dif
ferent way. It is quite evident that the
transition from the square OAMB to
the rhomb OA*M*B* can be achieved
by pressing the square along the di
rection AB, with simultaneous
stretching along the direction OM. It
means that pure shear can be consid
ered (and can be realized) through the
superposition of two uniaxial exten
sion deformations (with different
signs).
From the point of view of continuum
mechanics, the difference between
simple and pure shear is not signifi
cant, since deformations occur in the
infinitely small volumes “at a point”
and the rotationof infinitesimal elements of a body as a whole has no effect onits
deformation. But in real materials this difference can appear to be essential, be
cause an act of deformation involves certain volumes which may include a large
number of molecules or their constituent parts. That is why rotation in simple
52 Deformation and deformation rate
Figure 3.6. Scheme of pure shear.
shear does influence the rheological behavior of deformable (in particular flow
ing) materials and is taken into consideration in formulating laws of deforma
tions in the formof time derivatives used to calculate the rate of deformation, as
mentioned above.
3.7 EXAMPLES
Unlike stress analysis, the calculation of deformation fields cannot be carried
out for an arbitrary scheme of loading because reaction of a material to an exter
nal force depends on inherent properties of a medium and its geometrical size
and shape. That is why calculation of deformation is possible only for materials
having established properties. The same force creates unlimited deformation in
a liquid and only small deformation in a steel object.
The deformation can be found, regardless of rheological properties of a mate
rial, only for homogeneous deformation fields. Some principle examples have
been already discussed in the preceding Sections of this Chapter, and here we
shall summarize the main results.
3.7.1 UNIAXIAL EXTENSION OF A BAR (BEAM, FIBER)
It is one of the most frequently met cases in technology (e.g., orientational ex
tension of fibers) and everyday life. Stress analysis of uniaxial extension was
discussed in Chapter 2. Now, we shall summarize the main relationships de
scribing deformation.
Let the extension ratio of a uniform bar loaded along its axis be equal to λ (ini
tial lengthl
o
, the lengthafter deformationl, the extensionratioλ =l/l
o
). The engi
neering measure of deformation, ε *, is (λ  1). If ε * << 1 then
ε ε
11
= *
In uniaxial extension, lateral contraction takes place, and its value is deter
mined by the Poisson ratio
ε ε µε µε
22 33 11
= = − = − *
In some cases, it is especially important to know the components of complete
deformation, for example, if we wish to divide the full deformation into plastic
and elastic parts (such problem is pertinent to fiber spinning technology where
A. Ya. Malkin 53
the maingoal is to produce highly oriented fibers). It is necessary to use the mea
sure of deformation which is additive to the prehistory of loading and the
Hencky measure of deformations, ε
H
, as already discussed, to satisfy the re
quirement. For uniaxial extension
ε ε λ
H
= ln(1+ *) = ln
In the case of large deformations, ε
11
component of the deformation tensor has
the following structure:
ε ε ε λ λ λ
11
2 2 2
= *+
1
2
* = ( 1) +
1
2
( 1) =
1
2
( 1) − − −
Inapplications of the theory of large deformations to rubbers andrubbery poly
meric solutions, the Cauchy  Green and Finger methods of large deformation
calculations are widely used. Their values in our case are as follows:
C = ; C =
11
2
11
1 2
λ λ
Other components of C
ij
and C
ij
1
tensors are expressed through deformations,
ε ε
22 33
and , depending on the Poisson ratio.
3.7.2 SHEAR
Shear deformations are very typical for all hydrodynamic problems, including
the flowof lowviscosity liquids (water, oil, gasoline), liquidlike and plastic ma
terials, such as paints, sealants, clay, polymer solutions and melts, colloids, and
many others. Besides, many engineering applications rely on shear: twisting of
bars and tubes, cutting and threading are operations in which shear plays a
dominant role.
Main theoretical results concerning large deformations in shear were dis
cussed in detail in the last section of this Chapter and need not be repeated.
Shear rate, determining peculiarities of flow, may have variable impact even
under the same geometrical conditions and stress, depending on rheological
properties of a medium. Hence, only for homogeneous flowcan the shear rate be
estimated beforehand. Such flowoccurs in a very thin gap between two parallel
surfaces, with one of them fixed and the other moving with constant velocity, v.
54 Deformation and deformation rate
This condition is typical for flow in narrow gaps of bearings, and more impor
tant, it is widely used for measurement of rheological properties of various liq
uids in socalled rotational viscometers.
If the width of a gap, h, between surfaces moving in parallel to each other is
small, the shear rate, & γ, in a flowing liquid is calculated as
& γ = v/h
This formula also applies whenbothsurfaces are curvedbut the size of the gapis
much smaller than the radius of curvature; for example, if flow occurs in a very
narrowgapbetweentwo coaxial cylinders, one of whichis rotating withconstant
velocity.
3.7.3 PLANE DEFORMATION (STRAIN) STATE
Plane (twodimensional) stress and deformation (strain) state appears in thin
items, stretching films, membranes, shells, and so on. The stress fields for some
typical situations have been analyzed in Chapter 2. The calculation of the defor
mation field, regardless of rheological properties of matter, can be performed for
homogeneous static (equilibrium) state (e.g., a sphere (balloon) filled with gas,
having known pressure, up to the certain size).
Let the initial radius of a balloon be R
o
, and after increase of inner pressure the
radius becomes R. The initial width of a cover is δ
o
and δ
o
<< R
o
. The extension
ratio equals λ = R/R
o
. The directions along the radius of a sphere and tangential
to its surface are principal directions because shear stresses and deformations
are absent in thin shells, as discussed in Chapter 2.
The surface of the cover increases as a result of deformations, and for
(R − R
o
)/R
o
<<1 we have:
ε ε λ
2 3
o
o
= =
r R
R
= 1
−
−
where the directions 2 and 3 are tangential to the surface of the cover.
The third principal deformation, ε
1
, (the direction 1 is along the radius) can be
calculated using Eq 3.21, considering volumes of a material before and after de
formation. It is easily seen that in the case under discussion
A. Ya. Malkin 55
∆V/V = 1  (R
2
δ/R
o
2
δ
o
)
It means that
R R = 2
2
o
2
o
δ δ µ
and
δ δ µ
µ
λ
o o
2
2
= 2 (R R) =
2
Then
ε δ δ δ
µ
λ
1 o o
2
= ( ) =
2
1 − −
If volume of a material under deformations is constant (for example, if the
cover is made out of rubber), µ = 0.5 and we have
ε
λ
1
2
=
1
1 −
3.7.4 THREEDIMENSIONAL DEFORMED STATE
Many engineering applications can benefit from analysis of these relation
ships. Important to note is that consideration must be given to the real rheologi
cal properties of the material in question. Some general principles are worth
citing because they apply to analysis of large deformations of rubbers.
If the values of principal extension ratios are λ λ λ
1 2 3
, ,and , or the engineering
deformations along principal axes are
ε λ
i i
*= 1 −
then the values of the CauchyGreen and Finger tensors are:
56 Deformation and deformation rate
C = ; C = ; C =
1 1
2
2 2
2
3 3
2
λ λ λ
C = ; C = ; C =
1
1
1
2
2
1
2
2
3
1
3
2
λ λ λ
The first invariants of C and C
1
tensors are
C = ( ) and C = ( )
I 1 2 3
2
II
1
1 2 3
2
λ λ λ λ λ λ
As discussed above (see Eq 3.17), the equality λ λ λ
1 2 3
1 = means that deforma
tion proceeds without changes of volume. Hence the condition of constant vol
ume in threedimensional deformations of arbitrary type is: C
I
= C
II
1
= 1.
3.8 CONCLUDING REMARKS
Action of outer forces results in displacement of the points of continuum. If
displacements are inhomogeneous throughout a body, and relative displace
ments appear, they lead to deformations, which are the consequence of
changes of infinitesimal distances between different points inside a body. Dis
placement is a vector, but relative displacement and deformation are objects of
tensorial nature, because to describe them both it is necessary to operate with
two vectors. The relative displacement is described by a radiusvector of two
points for which displacement is considered, and the deformation by a vector of
displacement and a radiusvector of a point, where the displacement occurs.
Deformation is only a part of relative displacement, which also includes rota
tion of elements of a body as a whole.
Deformations can be small (or infinitesimally small) or large. The boundary
is determined by the value of relative displacement (or gradient of displace
ment), which is a dimensionless value. If this value is small (<< 1), it is reason
able to neglect the square of this value in comparison with the value itself. One
can thus neglect all quadratic terms included in the relationship. In this case,
deformations can be treated as infinitesimally small.
If large deformations are considered, some new effects appear. First of all,
physical phenomena occur at a site which moves and during deformation va
cates its initial position. Description of all occurrences (including deformation
itself) must be done in relation to a moving point. An observer, carrying out ex
periments with a material, follows its behavior and treats the results of mea
surements in a fixed coordinate system. Hence it is necessary to know the rules
A. Ya. Malkin 57
of transformations and the tensor values used for projecting deformations from
a moving to a fixed coordinate system.
Large deformations are characterized by special measures of deformation,
such as the Hencky measure (a logarithmic measure subjective to additivity
rule), Cauchy  Green, and Finger tensors of large deformations.
Time derivative of displacement of a point is its velocity, time derivative of rel
ative displacement is a gradient of velocity, and time derivative of deformation
is rate of deformation. Time derivatives of tensors are also tensors, and for
calculation of the rate of deformation, special rules exist which take into consid
eration large deformations and movement of a deforming site in space. Gradient
of velocity is a sum of rate of deformation and vorticity tensor as elements of a
body which can not only deform but simultaneously rotate it.
In the process of uniaxial longitudinal extension, a body undergoes lateral
compression. The ratio of relative changes of lateral and longitudinal sizes is
called the Poisson ratio, which is an inherent property of a material. For the
range of small deformations the volume of a body remains unchangedif the Pois
son ratio equals 0.5, but in large deformations this simple rule is not obeyed.
There is a special interesting case of deformationwhenvolume changes are not
taking place, which is a simple shear. At large shear deformations, diagonal
components of the deformation tensor appear, and they lead to some effects of a
second order, such as elongation of long items at their twisting (Poynting ef
fect). Simple shear is accompanied by rotation of elementary volumes in space.
It may reflect behavior of a material. In order to exclude rotation, it is necessary
to apply pure shear inwhichrotationdoes not exist. This type of deformationis
equivalent to a twodimensional situation of superposition of extension and
compression in mutually perpendicular directions.
3.9 REFERENCES
1. H. Z. Hencky, Angew. Math. Mech., 5, 144 (1925). Concept introduced by G. Kirchhoff,
Acad. Wiss. Wien Sitzungsberichte, (IIa), 103 (1894).
2. J. L. White and A. B. Metzner, J. Appl. Polym. Sci., 7, 1867 (1963); J. L. White,
J. Appl. Polym. Sci., 8, 2339 (1964); Rubber Chem. Techn., 42, 257 (1969).
3. A. J. B. de St. Venant, Mémoire sur équilibre des corps solides, dous les limits de leur
élasticité, et sur les conditions de lèur resistance quond es désplacements êpouvés par
leurs points ne sont par trés petit, C. R. Acad. Sci., Paris, 24, 1847.
4. J. Finger, Acad. Wiss. Wien Sitzungsberichte, (IIa), 103 (1884).
5. S. Zaremba, Bull. Int. Acad. Sci., Cracovie, 594, 614 (1903).
6. F. Cosserat, Thèorie des corps deformable, Paris, 1909.
58 Deformation and deformation rate
7. G. Jaumann, Acad. Wiss. Wien Sitzungsberichte, 120, 385 (1911).
8. M. Biot, Theory of elasticity with large displacements and rotations, Proc. 5th Int.
Congr. Appl. Mech., 1939.
9. R. S. Rivlin, Phyl. Trans. Roy. Soc. Lnd., Ser. A, 240, 459, 491, 509 (1948);
241, 379 (1949); 242, 173 (1950); 243, 251 (1951); Proc. Roy. Soc., A195, 463 (1949).
10. A. E. Green and J. E. Adkins, Large Elastic Deformations, Oxford University Press,
London, 1960.
11. A. S. Lodge, Elastic Liquids, Academic Press, London, 1964.
A. Ya. Malkin 59
4
RHEOLOGICAL
EQUATIONS OF STATE
4.1 MAIN RHEOLOGICAL EFFECTS
The concept of rheological equation of state (or constitutive equation)
occupies the central position in modern rheology. It is a relationship between
stresses acting at a point and deformations occurring as a result of their action.
Such a relationship determines all mechanical phenomena which can be ex
pected in the observation of mechanical behavior of a material. Rheological
equations of state serve the purpose of understanding and describing qualita
tively and (the most desirable) quantitatively various “anomalous” effects ob
served in real life for real materials. Some macroforms of these effects were
mentioned in Chapter 1 and they are now described in rheological language in
terms of stresses, deformations, and rates of deformation.
The number of various rheological “anomalies” is large; any kind of deforma
tionof material whichdoes not obey the simplest, classical rheological equations
(Newton and Hooke Laws) inevitably leads to different, new qualitative, or at
least quantitative, phenomena which are not described by the concept of a New
tonian fluid and a Hookean solid body. Each of these phenomena can be consid
ered as a “rheological effect”. However, there are several fundamental
experiments which definitely indicate that material is either “classic” or “rheo
logical”. These experimental observations are discussed below.
A. Ya. Malkin 61
4.1.1 NONNEWTONIAN VISCOSITY
If we define viscosity, η, by Eq 1.1 as a ratio of shear stress, σ, and shear rate, & γ,
and then carry out measurements at different values of σ or & γ, the ratio σ γ&
should be constant because viscosity is a property of liquid. Liquids having con
stant viscosity for any & γ are called Newtonianliquids and their viscosity is called
Newtonianviscosity. In many real cases, the ratioσ γ& is not constant, and it
is called apparent (or nonNewtonian) viscosity, even though the same sym
bol, η, is used. Dependence of the apparent viscosity onshear stress or shear rate
is called flow curve. It can be displayed in any of three coordinate systems,
η σ η γ σ γ − − − , ,or , & & as shown in Figure 4.1. The apparent viscosity decreases in
this example, and such effect is frequently called shear thinning. This is the
most typical case, but viscosity can also increase with shear rate increasing (the
socalled shearthickening). Sometimes, viscosity decreases or increases (for
the same material) in a different range of shear rate.
In many applications, it is important to know how apparent viscosity changes
when shear rates (and stresses) are changing in a very wide range. In order to
make this dependence more visual, logarithmic scales are frequently used. The
graph constructed in log& γ  logσ coordinates is also called a flow curve. The flow
curve of any Newtonian liquid is a straight line inclined by 45
o
to both axis;
therefore measurement points fulfill the condition of constancy of the σ γ& ra
tio.
62 Rheological equations of state
Figure 4.1. Different images of a flow curve: dependencies η σ ( )  a, η γ (
&
)  b and σ γ (
&
)  c.
NonNewtonian behav
ior of a liquid was, for the
first time, observed by
Ostwald
1
for colloid dis
persions, and was ex
plained by the changes of
a structure of colloid as a
result of deformation.
Some authors continue
to call the ratio σ γ& a
structure viscosity
(struktur Viskosität
1
),
even though the origin of
this effect is not neces
sary related to the rup
ture of a “structure” of a
flowing liquid.
Some typical examples
of nonNewtonianbehav
ior are given in Figures
4.2 and 4.3 for polymeric
systems and in Figure
4.4 for a bentonite solu
tion. In all cases shown
in these Figures, the ef
fect of nonNewtonian
flow is very pronounced,
though it appears in dif
ferent forms: as a grad
ual decrease of apparent
viscosity in Figures 4.2
and 4.3, and as a sudden
jump from very high to
very low viscosity in Fig
ure 4.4.
A. Ya. Malkin 63
Figure 4.2. Flow curves of polybutadiene solutions in methyl
naphthalene. Upper line  flow curve of a pure solvent. Lower
curve  flowcurve of a pure polymer. All other curves are drawn
for solutions. Concentration of the polymer in weight percent
age as labeled. T = 25
o
C.
One of the main problems in description of flowcurves is the existence of limit
ing values of apparent viscosity at σ → 0 or & γ → 0, and at σ → ∞ and & γ → ∞,
which are important to consider in interpretation of the physical meaning of
nonNewtonian behavior and in quantitative description of a flow curve.
Flowcurves in Figure 4.2 are typical of polymer solutions. The solvent used be
haves like a Newtonianliquid (flowcurve is a straight line inclined by 45
o
to both
axes). In rather dilute solutions, flowcurves display three regions. At lowshear
rates (formally at σ γ → → 0and 0 & ), Newtonian behavior is observed (straight
line inclined by 45
o
to both axes), and apparent viscosity corresponding to this
region of a flowcurve is called zeroshear or initial or maximumNewtonian
viscosity. Then the decrease of apparent viscosity (declining from the straight
line) is observed typical of nonNewtonianbehavior. Finally, the upper part of a
flow curve again has Newtonian behavior. The value of apparent viscosity at
these high shear rates and stresses (formally at σ γ → → 0and 0 & ) can be called
upper, limiting, or minimum Newtonian viscosity.
64 Rheological equations of state
Figure 4.3. Flow curve of a polyethylene melt. Experiments conducted for a typical polydisperse
polymer. Melt index of a sample was 2 g/10 min. T = 150
o
C.
Further increase of polymer concentration leads to increasingly more notice
able deviation fromNewtonian behavior, though in all cases the Newtonian vis
cosity, at low shear rates, is apparent. Highly concentrated solutions (30% and
higher) have a broader range of nonNewtonian behavior, followed by the flow
curve which becomes close to a vertical line. This behavior is particularly strong
for a pure polymer. It may be argued whether this region of the graph corre
sponds to real flowwith rapid decrease of apparent viscosity or it reflects other,
special type of behavior of a material, but undoubtedly these experimental ob
servations demonstrate peculiar rheological properties of these media.
There is no doubt that the initial Newtonian viscosity region exists for all, in
cluding very concentrated, solutions. Also, the upper Newtonian region of flow
curves cannot be reached (or maybe does not exist) for concentrated solutions.
The general reason for this is a loss of flow stability at high shear rates (a very
close analogy of this behavior is a wellknown transition fromlaminar to turbu
lent flow for regular liquids).
Another example of rheological properties is represented inFigure 4.3 for poly
mer melt. A continuous and gradual decrease of apparent viscosity occurs in a
A. Ya. Malkin 65
Figure 4.4. NonNewtonian viscous behavior of 10%suspension of natural bentonite (in log  log
&
γ σ
and η σ − coordinates). Limiting values of apparent viscosity at shear stresses σ → 0 (η = 0.95
mPas) andat σ → ∞(η=9.3 MPas) are shown. After L. A. Abduraghimova, P. A. Rehbinder, andN.
N. SerbSerbina, Kolloid Zh., 17 (3), 184  195 (1955).
very wide range of shear rates. The whole decrease of apparent viscosity exceeds
1000 times in comparison with the initial value. The initial Newtonian region in
the flow curve appears in this Figure only as a hint; it may even be suspected
that this branch does exist.
Figure 4.4 represents a flow curve with a very sharp drop of viscosity at some
value of shear stress, σ
y
, or in a narrowrange of shear stresses. The initial New
tonian viscosity, η
o
, can also be found here as a limit of η σ at 0 → . The magni
tude of η
o
exceeds the apparent viscosity, in other regions, by several decimal
orders of magnitude. In fact, viscosity drops by 8 decimal orders of magnitude,
from0.95 MPa⋅s to 9.3 mPa⋅s. That is why it is reasonable to treat the behavior of
a material atσ σ <<
y
as solidlike (eventhoughthe material is a liquid and flows
even though its viscosity is very high). The transition throughσ
y
might be con
sidered as a transition from solidlike to liquidlike behavior, and only the part
of the flow curve at σ σ >
y
as the flow curve.
The materials having sharp transition from solidlike to liquidlike behavior,
at sufficiently high shear stresses to cause flow, are called viscoplastics, and
the transitionstress is called yieldstress (or yield point). The flowcurve inFig
ure 4.4 can be treated as a flow curve of a nonNewtonian liquid with rapid vis
cosity decrease or as a dependence of apparent viscosity on shear stress,
characteristic for viscoplastic bodies. Both definitions are reasonable. In many
cases, it is very difficult to find a proper assignment for experimentally observed
viscosity versus shear stress dependence of real materials rapidly changing
their structure under deformation.
Many attempts were made to describe flowcurves of various materials by ana
lytical functions of different type, both on theoretical and empirical levels. For
the flow curves with distinctly expressed range of initial Newtonian viscosity,
the following equations are frequently applied:
Cross equation:
2
η
η
λγ
=
1+ 
o
m
&
[4.1]
Carreau equation:
3
η
η
λγ
=
[1+ ( ) ]
o
2 p
&
[4.2]
Yasuda et al. equation:
4
η
η
λγ
=
[1+ ( ) ]
o
a (n1)/ a
&
[4.3]
66 Rheological equations of state
Vinogradov  Malkin equation:
5
η
η
γ γ
α α
=
1+ A + B
o
2
& &
[4.4]
In all equations, η is apparent viscosity, depending on shear rate, η
o
is
zeroshear viscosity, all other symbols are empirical or semiempirical con
stants.
All the equations are similar in their structure. They differ in a number of pa
rameters: two in Eqs 4.1 and 4.2, and three in Eqs 4.3 and 4.4. It is interesting to
emphasize two main peculiarities of these equations: all have a limit at & γ → 0
equal to η
o
. At sufficiently high values of shear rate, they transit to the socalled
power law (Ostwald  de Waele equation),
6
which can be written as
σ γ = K
n
& [4.5]
where K and n are empirical parameters.
All equations show that, at & γ → ∞, apparent viscosity diminishes to zero. It
means that it was assumed that there is a great decrease in apparent viscosity,
when shear rate increases, in comparison with η
o
, so that the limiting value of
apparent viscosity at & γ → ∞ is negligibly small. There are situations (for exam
ple, relatively dilute polymer solutions) when the total decrease in apparent vis
cosity is not large, and the minimal value of apparent viscosity at & γ → ∞ is
frequently observed. In many cases, the possibility to reach the limiting viscos
ity is restricted because, at very high shear rates, flowinstabilities of a different
kind appear.
Discussing the problem of apparent viscosity, it is important to note that the
definition of viscosity applies to steady flow (no timerelated changes). In some
cases it is important to consider viscosity in transient regimes of shear deforma
tions. For pure viscous liquids, nothing is changing in this case. In other cases, & γ
must be treated, not as a rate of full deformation, but only as a rate of flow, i.e.,
rate of irreversible deformation. If the deformation is reversible (elastic), it has
nothing in common with viscous flow and definition of viscosity. Thus, in tran
sient flow, only a part of deformation is related to the flow; the rate of this defor
mation must be taken into account in calculating viscosity.
The flow curve measurements have various applications. Two of them are of
primary value. First, it is always necessary to know viscous properties of a real
material to solve any hydrodynamic problem related to flow of the material  in
A. Ya. Malkin 67
particular, to design processing equipment and predict conditions of its use in
practice (e.g., calculation of rate of flow and pressure drop). Second, the flow
curve reflects chemical content and/or physical structure of a material, and as
such it can be used as a method of analysis of material quality.
4.1.2 PLASTIC BEHAVIOR
Viscoplasticity can be for
mally treated as a viscous flow:
viscosity is infinite at σ σ <
y
,
and it decreases in a very nar
row range of shear stress near
σ
y
, as discussed above. Plastic
material cannot be deformed at
σ σ <
y
, and it flows at σ σ >
y
.
The yield stress, σ
y
, is charac
terized by a rapid change of vis
cosity at σ σ →
y
(Figure 4.5).
For some materials, such as
many pastes, greases,
bentonites, and paints, this pat
tern of behavior is very close to
reality (see Figure 4.4). For
other materials  for example, polymer melts containing solid filler, rubber com
pounds, sealants  the transition through the yield stress appears milder, as
demonstrated in Figure 4.6.
Formal descriptionof viscoplastic behavior is based ona model of abrupt jump
of viscosity at σ
y
and existence of yield stress. Two analytical equations are usu
ally used to characterize viscoplastic behavior:
Bingham equation
7
σ σ η γ = +
y p
& at σ σ <
y
[4.7]
Casson equation
8
σ σ γ
1 2 /
& = +
y
1/ 2 1/ 2
K at σ σ <
y
[4.8]
whereσ
y
is the yield stress, and η
p
and Kare empirical constants. The constant
η
p
is sometimes called the “plastic” or Bingham viscosity.
Eq 4.7 represents a linear model. It predicts the decrease of apparent viscosity
in the flow range:
68 Rheological equations of state
Figure 4.5. Characteristic “flow curve” for a
viscoplastic medium in
&
γ σ − (a) and η σ − (b) coordi
nates.
η
σ
γ
η
σ
γ
= = +
p
y
& &
[4.9]
The apparent viscosity decreases when the shear rate increases, as shown in
Figure 4.5 b.
If viscosity at σ σ >
y
is constant, the behavior is not described by the Bingham
equation and can be represented by the following equation:
η σ σ η η σ σ = ∞ = at < at >
y y 0
[4.10]
A. Ya. Malkin 69
Figure 4.6. Flow curve for a filled polymer melt  polyisobutylene containing 5 wt% carbon black,
60
o
C  demonstrating gradual approach of the yield point.
The existence of a range of low stresses in which a viscoplastic material is
solidlike leads to rather peculiar properties. If suchmaterial is pressed through
a round channel, the stress at the axis equals zero. In fact, there is a core in the
entire central zone where shear stress is very low. It means that there is a zone,
in the central part of a channel, where shear stress is lower than σ
y
; therefore
this part of viscoplastic material does not flow but moves as a solid plug. Such
behavior is frequently called plugflow.
The termplasticity
9
(andthe concept of plastic behavior) is also usedfor solids
which can be elastic (up to the yield point), and then deformto unlimited extent
when this critical stress is reached. The term“flow” has a rather peculiar mean
ing for such materials as metals; nevertheless, they really flow (i.e., are de
formed irreversibly) atσ σ >
y
. The plastic behavior of solids atσ σ >
y
is essential
in such technological operations as punching of golden articles (coins and so on)
or rolling of ingot steel.
In summary, it is necessary to emphasize that Eqs 4.1 through 4.10 are not
rheological equations of state, they only contain empirical description of experi
mental data obtained in unidimensional shear deformations.
4.1.3 WEISSENBERG EFFECT
Weissenberg has described a set of “strange” pictures of behavior of some liq
uids (Figure 4.7).
10
If a rod is rotated inside a “rheological” liquid, such a liquid,
instead of being displaced from the rotor by centrifugal force towards the walls
of a vessel, begins to wind around the rotor and climb it (Figure 4.7  case 1). In
the case of two coaxial cylinders (inner hollow), the rotation of the outer cylinder
forces liquid into the inner cylinder (Figure 4.7  case 2). Another characteristic
example concerns liquid between two parallel discs. When the outer disc is ro
tatedarounda commonaxis, the inner disc is liftedupby normal force generated
due to rotation (Figure 4.7  case 3), and if a hole would be made in the center of
one of the discs, this “strange” liquid instead of being removed fromthe space be
tween the discs to the periphery of the discs, is pressed through the hole. Such
behavior means that the force not only acts normal to the surfaces of the discs
but in the radial direction to the central axis as well.
The abovementioned and some other related observations are known under
the general name of the Weissenberg effect. Phenomena associated with this
effect are very common in technological applications, because reactors with ro
tating mixing elements, mixers of different geometry and type, are regular
70 Rheological equations of state
A. Ya. Malkin 71
Figure 4.7. Typical phenomena usually associated with the Weissenberg effect: a rod rotating in a
liquid (1); rotating outer cylinder with liquid filling the center of a hollow cylinder (2); a liquid be
tween two parallel rotating disks (3). (Continued on the next page.)
equipment in various branches of the chemical, food and pharmaceutical indus
tries. Moreover, the last example of the Weissenberg effect shown in Figure 4.7
(case 3) was used to design a special type of machine for polymer processing, the
socalled screwless extruder. In this design, a material is mixed between two
discs and pressed through a nozzle by an action of forces originated from the
Weissenberg effect. Normal forces appearing due to rotation of parallel discs
also give additional support in slide bearings if a “rheological” liquid is used as a
lubricant. Some investigators think that the Weissenberg effect provides the
ability of articulations in biological organisms and that deficiency in this phe
nomenon leads to an illness (“squeak in joints”).
It is interesting to understand the rheological origin of this effects, i.e., what
happens at the reference point. The commonfeature of all phenomena is appear
ance of forces acting in the direction of shear and in the perpendicular direction.
It is equivalent to appearance of normal stresses inshear, eventhough, at the
72 Rheological equations of state
Figure 4.7. Continuation; see caption on the previous page.
first sight, it would be reasonable to suspect that only shear stress acts in a sim
ple shear. This is true for many liquids, but not always. Normal stress (diagonal
component of the stress tensor) also acts, and the diagramof stresses is shownin
Figure 4.8.
It is possible to anticipate that normal components of stress tensor are related
to appearance of a diagonal component inthe tensor of large deformations. Their
existence can be explained by large elastic deformations developed in flow (it
may be argued whether this explanation is general, but undoubtedly the large
elastic deformations lead to normal stresses). The appearance of normal
stresses in a simple shear is a main rheological reason for the Weissenberg ef
fect.
In order to characterize the phenomenon, not absolute values of normal
stresses but their differences are important. If, for example, hydrostatic pres
sure is superimposed, it will change all normal components of the stress tensor
but wouldnot influence flow. (If this pressure is not very high, it is possible to ne
glect the compressibility of a liquid  true in many real situations.) The differ
ences of normal stresses are defined as follows:
first difference of normal stresses: σ σ σ
1 11 22
= −
second difference of normal stresses: σ σ σ
2 22 33
= −
A. Ya. Malkin 73
Figure 4.8. Notation of normal stresses at plane simple shear.
(σ σ
1 2
and are not invariants of the stress tensor, though they are written in the
same manner).
In rheological literature, very often, not σ σ
1 2
and are used but their coeffi
cients (analogous to the use of viscosity coefficient instead of shear stress). The
first and the second normal stress coefficients are defined as
Ψ
−
Ψ
−
1
11 22
2
2
22 33
2
= ; =
σ σ
γ
σ σ
γ & &
[4.11]
Normal stress in shear flowis an effect of the second order, and that is why, at
least in first approximation, σ σ
1 2
and are proportional to squared shear stress,
σ
2
, and coefficients of normal stresses are proportional to η
2
. In all known cases,
σ σ
1 2
>> . Normal stress as an effect of the second order is much smaller than
shear stress at lowshear rates, or to be more precise: ( ) <<1
11 22 12
σ σ σ − . With
shear rate increasing, the normal stresses grow very quickly (proportional to
squared shear rate), and at high shear rate, normal stresses become larger than
shear stress, therefore they are critical for analysis of flow of some liquids (for
example, concentrated polymer solutions and melts).
4.1.4 TRANSIENT DEFORMATIONS IN SHEAR (OF LIQUIDS)
For regular liquids, the stepwise setting of constant shear rate leads to an im
mediate beginning of flow. Shear stress, which maintains the steady flow, re
mains constant all the time (eliminating inertial effects). After the cessation of
flow, stress instantaneously drops to zero. There are some liquids (and they are
the object of rheological studies) for which development and disappearance of
stresses is far from the simplest scheme.
Figure 4.9 demonstrates the effect of stepwise setting of constant shear rate.
11
The left side of the diagramrepresents “regular” and the right side “rheological”
liquids. The main observations for the latter are as follows:
• at lowshear rate, there is a very prolonged time interval of slowly developing
shear stresses, and this interval becomes shorter if shear rate is increased
• at high shear rates, shear stresses pass through a maximum (sometimes
several maxima can be observed) before reaching the state of steady flow
• after sudden cessation of flow, shear stress decays (relaxes); the initial relax
ation rate increases with increasing initial shear rate.
74 Rheological equations of state
Besides this complex behavior,
the Weissenberg effect (normal
stresses at simple shear) also ex
ists. The evolution of normal
stresses (regardless of σ σ
1 2
and ),
before the steady state and during
relaxation, is similar to the devel
opment and decay of shear
stresses. The main peculiarity
consists of much slower change of
normal thanshear stress, either in
prestationary (presteady) state
of deformations or during relax
ation.
12
This effect is illustrated in
Figure 4.10 for relatively low
shear rate when a maximum of
stresses is not attained.
Transient behavior is also observed at other types of deformations (not only at
constant shear rate). If shear stress is set constant, then rate of deformation will
be changing intime ina manner showninFigure 4.11. The steady flowregime is
reached after a transient range of deformation, when shear rate is changing due
A. Ya. Malkin 75
Figure 4.9. Development of shear stresses at preset constant shear rate for regular (a) and “rheo
logical” (b) liquids.
Figure 4.10. Comparison of development (at con
stant shear rate) and decay (after cessation of
flow) of shear and normal stresses.
to a change of a relative effect of plastic
and elastic components, along with de
formation rate.
Transient rheological behavior is a
very characteristic time effect, leading
to a complex relationship between
stress and rate of deformation. The
most evident manifestations of this ef
fect can be observed at preset constant
stress or shear rate. The reasons for the
effects can vary, but the main models of
the behavior are:
• thixotropic (rheopectic) phenomena
• viscoelastic behavior of a material.
Both typical phenomena are discussed
in separate Sections below. Important
practical applications are numerous, es
pecially in cases when time for tran
sient behavior is rather long and
comparable with duration of flow. For
example, it is applicable to flowin short
dies, suddenchanges of the diameter of a channel, or local hindrances inouter or
inner flows. In all these, and many other cases, it would be incorrect to charac
terize properties of a liquid by its flowcurve alone, i.e., the relationship between
stresses and rates of deformation, measured only at “equilibrium” conditions
(after completion of transient processes). It is therefore important to under
stand the reasons for these effects in different media and describe them in rela
tion to the whole complexity of the properties of matter.
4.1.5 UNIAXIAL EXTENSION
Uniaxial extension of liquids is a very important method of deformation en
countered infiber formation, orientational drawing, and formationof thinfilms.
From a theoretical point of view, uniaxial extension differs geometrically from
deformation in shear flow. In shear, the tangential stress determines behavior
of a material, whereas in uniaxial extension only normal stresses are applied. It
is thus very important to understand howdifferent materials manifest their in
76 Rheological equations of state
Figure 4.11. Development of shear rate at
constant stress for regular (a) and “rheo
logical” (b) liquids. Dotted lines show
change of elastic (1) and plastic (2) compo
nents of deformation.
herent properties under varying conditions of loading to construct threedimen
sional rheological equations of state.
If a liquidis stretched, it flows (similar to shearing), andthe elongational vis
cosity, λ, can be determined as a ratio of normal stress, σ
E
, to the gradient of ve
locity, & ε (equal, in this case, to the rate of axial deformation):
λ
σ
ε
=
E
&
[4.12]
For Newtonian liquids, their elongational viscosity equals 3η. The equality
λ η =3 [4.13]
is called the Trouton law and the value λ is called the Trouton viscosity.
13
In the range of lowdeformation rates, Eq 4.13 is valid as a limiting case for any
liquid. For some liquids, increase in the rate of deformation leads to a change of
their elongational viscosity. As a rule, the elongational viscosity increases at
higher rates of deformation, but opposite cases also have been observed.
The most appropriate method of elongational viscosity measurement would be
to drawa sample until a regime of steady state flowis reached, and then normal
stress and rate of deformation are measured to calculate elongational viscosity
according to its rigorous definition expressed by Eq 4.12. Unfortunately, in most
cases, such an obvious procedure is not applicable because the stretched mate
rial usually ruptures before a steady state is reached. The rupture of samples at
high draw ratios (factor limiting experiments in extension) is a principle differ
ence between shearing, which can continue for an unlimited time, and exten
sion. In discussion of experimental data obtained for flowin uniaxial extension,
it must be remembered that data (as a rule) relate to the transient behavior of a
material.
A general picture of normal stress distribution during extension of “rheologi
cal” liquid at different rates of deformation is given in Figure 4.12. At low rates
of extension (curve 1), stress reaches constant level, corresponding to steady
elongational flow with constant Trouton viscosity. But at high rates of exten
sion, there is no limiting state related to a viscous flowand stress grows with ac
celeration (curve 2) up to the rupture of the sample.
14
The latter case is a typical
A. Ya. Malkin 77
example of transient behavior and it is
inappropriate to treat curve 2 in Figure
4.12 as a reflection of viscosity growth in
extension.
It is worth noting that rupture of “rheo
logical” media also occurs in some differ
ent ways than ultimate breaking of
regular materials. Schematically, they
are pictured in Figure 4.13: the upper
drawing shows that rupture of ordinary
material occurs after a continuous pro
cess of sample flow, leading to its rupture
in the weakest section. The next drawing
(b) relates to “rheological” liquid (e.g.,
rubber glue): during stretching, spheri
cal droplets are formed along the stream
and rupture follows. The lower drawing
(c) shows rupture of stretched solids.
Regular material deforms as shown in
Figure 4.13a, but “rheological” solid
forms a sharp local contraction  neck
ing  and following deformation, occurs
through a transition froma parent mate
rial to a neck.
4.1.6 INSTABILITIES AND SECONDARY FLOWS
15
Stability of flowis of general interest in
numerous applications: sailing ships,
pipelines for liquid materials (water, oil
products, etc.), flow of material in dies,
paint milling, water spraying, produc
tion of plastic parts with high quality
surfaces, and so on.
In “regular” liquids, instabilities ap
pear as a result of capillary or inertial
forces. The first reason leads to surface
78 Rheological equations of state
Figure 4.12. Development of stresses in
uniaxial extension of “rheological” liquid
at low(curve 1) and high(curve 2) rates of
deformation.
Figure 4.13. Drawings demonstrating
characteristic modes of deformation in
stretching of a regular material (a), “rhe
ological” liquid (b) and solid (c).
effects, such as breaking up a streaminto many droplets. The second reason is a
base of the socalled Reynolds turbulence, which appears as a chaotic movement
of liquid particles in any flow. Reynolds turbulence occurs when inertial forces
exceed viscous damping of occasional disturbances. Turbulent flowoccurs when
and if the critical value of the Reynolds Number, Re, is exceeded. Re is deter
mined as
Re =
Vdρ
η
[4.14]
where V is characteristic velocity, d characteristic linear size, ηviscosity, and ρ
density.
The critical value of the Reynolds Number, corresponding to possible transi
tion from laminar to turbulent flow in cylindrical channel, is about 2300 (the
Reynolds Number, like any other criteria of similarity, is a dimensionless
value).
Reynolds (inertial) turbulence canalso take place inthe flowof nonNewtonian
liquids, but the most interesting fact is that in the flow of “rheological” liquids,
unexpected effects appear. In some cases, flowbecomes unstable at values of the
Reynolds Number different from that characteristic for regular liquids at the
equivalent conditions of flow. It indicates that different mechanisms of instabil
ity can exist. Since the critical value of the Reynolds Number reflects viscous
properties of liquid, these newmechanisms of instability must reflect other rhe
ological properties of material. Then, the main problem consists of understand
ing these mechanisms and correlating them with rheological properties of
media.
Instabilities of different types accompany many technological processes. For
example, they are the cause of haziness of extruded films, rough surface of cable
insulation, waviness of fibers in spinning, and so on. Instabilities in flow have
been observed for various “rheological” liquids and can manifest themselves in
different forms. There is a common opinion that the general reason for instabil
ity of many “rheological” liquids is their elasticity and viscoelastic effects  a pri
mary characteristic of polymeric liquids (melts and solutions).
The concept of viscoelasticity (Chapter 7) requires us to consider at least one
parameter reflecting elastic properties of material in addition to its viscosity. It
can be the modulus of elasticity, E, but it is preferable to use a measure of the
A. Ya. Malkin 79
rate of inherent rearrangement processes in a material (not specifying its na
ture). This time constant, called relaxation time, θ, is defined, at least for di
mensional reasons, as
θ
η
=
E
[4.15]
This value must be used as a second (additional to viscosity) characteristic prop
erty of a liquid.
It is therefore reasonable to introduce a new dimensionless criterion to mea
sure a ratio betweenviscous and elastic forces inflow, suchas the Weissenberg
Number, We, defined as
We =
V
d
θ
[4.16]
The Weissenberg Number is close but not quite equivalent to the Deborah
Number, De:
De =
T
θ
[4.17]
where Tis a characteristic time of flow. The value (V/d) can be treated as a char
acteristic time constant but it is more reasonable to use the Weissenberg num
ber in steady flowand the Deborah Number in timedepending flows, where Tis
a time factor for transient flows.
Phenomena of instability in flowof “rheological” liquids can be manifested dif
ferently, depending on the geometrical mode of flowand the inherent properties
of a liquid. However, the following manifestations are the most characteristic:
• extrudate distortions (sometimes called “melt fracture”)
• secondary flows (flows in straight channels of a simple geometrical form,
such as flow between coaxial cylinders) superimposed on primary flow
• interfacial and surface instabilities (boundary distortions in flow of
multicomponent systems, breaking free streams, and so on)
• rheological phenomenon in inertial turbulence (Toms effect).
80 Rheological equations of state
4.1.6.1 Extrudate Distortions (Melt Fracture)
16
Extrudate distortions are observedwhenpolymer inthe formof a concentrated
solution or melt is forced through a die (orifice or capillary) and when free recov
ery of deformations, stored during constrained flow in channels, occurs. This
type of instability is of special importance for polymer processing because it lim
its the desired tendency to increase production rate. Besides the discussion of
reasons and quantitative description of boundaries of stability (directly related
to rheological properties of matter), it is an interesting general problem of con
tinuous mechanics, andas such, it was treatedinnumerous theoretical studies.
Photographs inFigure 4.14 showtwo situations. The left picture demonstrates
a stream leaving an orifice (visible at the upper part of the photograph) at low
A. Ya. Malkin 81
Figure 4.14. Instability in flow appearing in the form of regular (screwlike) defects: left  smooth
stream in stable flow; right  instable flow.
speed. The flowis stable and the surface of the streamis quite smooth. The right
photographdemonstrates what happens to the same material whenthe speed of
flow exceeds some limit. The regular defects resembling a screw appear on the
surface as a manifestationof instability. Inthis case, the instability arises as pe
riodic oscillation.
Photographs in Figure 4.15 showmore severe consequences of flowinstability.
The photographs show frozen samples of streams leaving a die. The shear rate
was increasing from left to right. During the flow inside the orifice, large inher
ent forces (or energy) were stored in the material, and when the polymer melt
was released froma die (capillary or orifice) at high velocity, the streamdisinte
grated, fragmenting into separate elements.
Numerous observations, similar to those presented in Figures 4.14 and 4.15,
show that, as a rule, extrudate distortions start from slight skin defects. Then
they are enlarged to regular surface defects (sometimes called “sharkskin”),
82 Rheological equations of state
Figure 4.15. Instability of flowleading to disruption of a stream: transition fromleft to right corre
sponds to increase of velocity (shear rate).
forming gross regular variations of a crosssectional area and shape (sometimes
looking like a helical screw on extrudate) which can be an evident result of a
“stickslip” mechanism, when alternating rough and smooth zones appear on
the surface of an extrudate. Finally, the instability of this type reaches a formof
chaotic distortions and ruptures of stream, as documented in Figure 4.15, illus
trating the meaning of “melt fracture”. Many direct observations of flow lines
(made by markers suspended in a flowing liquid through transparent walls of a
channel) showed that movement of a liquid inside a channel at high velocities,
when an extrudate becomes irregular, is unstable and movement of markers is
chaotic. It is direct evidence of flow instability.
The appearance of gross distortions of periodic or aperiodic types in the flowof
polymers (melts and concentrated solutions) can be accompanied by an abrupt
jump of the flowrate  “spurt”  during flowthrough a capillary (die) under con
stant pressure.
17
This effect is explained by loss of fluidity and sliding along a
solid wall, due to relaxation transition of a linear polymer into a rubbery state.
This is the reason why “liquid” begins to behave, not like a fluid, but similar to a
solid, rubberlike material which does not flowbut slides as a plug along a chan
nel.
The main result of numerous experiments shows that instability in flowin the
formof “extrudate distortion” occurs at very lowvalues of the Reynolds Number,
sometimes as low as 10
5
, because viscosity of a melt is very high, and (most im
portant) the effect under discussion does not correlate with any definite value of
the Reynolds Number. It is therefore necessary to find an explanation of this ef
fect other than the Reynolds turbulence.
There are at least two causes for extrudate distortions. At relatively low flow
rates, surface distortions occur as a consequence of nonlinear effects in defor
mation of “rheological” liquids  such phenomena as their elasticity and/or nor
mal stress in shear flow. Gross extrudate distortions such as melt fracture are
related to a nonlinear phenomenon such as phase (or relaxation) transition.
The meltfracture instability appears at some critical value of the Weissenberg
Number, namely about 5. The exact value of the Weissenberg Number depends
on details of the method used for its estimation. In original publications, one can
find critical values of the Weissenberg Number in shear flows in the range from
1 to 10.
18
Perhaps the scatter of these values can be explained by difficulties in
determination of an exact moment when flow instability occurs and/or by diffi
culties in distinguishing between different mechanisms leading to similar fea
A. Ya. Malkin 83
tures of unstable flow. Indeed, strong nonlinear effects and phase (relaxation)
transition in flow can superimpose and therefore lead to somewhat deceiving
conclusions concerning quantitative criterion of instability.
Extrudate distortion is velocity dependent, and begins beyond some limiting
velocity of flow. Extrudate distortion has an industrial importance because it
limits the increase in flowrate, and thus, output in many technological applica
tions such as fiber spinning, extrusion, etc. The understanding of the principles
and controlling rheological parameters allows one to evaluate the processability
of materials and select them, based on laboratory data.
4.1.6.2 Secondary Flow
The initial stage of instability occurs due to the socalled secondary flow.
Secondary flow is formation of closed vortices in planes perpendicular to the di
rection of the main (primary) flow, governed by the movement of solid bound
aries in a liquid sample. For example, secondary flow in a straight cylindrical
channel produces circular flow lines in planes perpendicular to the axis of a
channel. Secondary flow does not appear in “rheological liquids” in channels
having a circular crosssection but can be found in channels with crosssections
of other geometrical forms.
Secondary flow increases resistance to flow, meaning that the energy con
sumption in transportation of “rheological” liquids is increased in comparison to
a regular liquid of the same viscosity. On increasing the flowrate, the secondary
flowcauses muchstronger instability, and that is why they are so closely related
to such gross effects as flow distortions.
The most wellknown case of secondary flow in Couette flow is called Taylor
instability.
19
It is shown in Figure 4.16 along with some other cases of second
ary flows. If a liquid is placed in a gap between two coaxial cylinders, and one of
them is rotated, the main flow takes place in a circular direction, and a second
ary flowforms closed flowlines, called Taylor cells (Figure 4.16a). Aquite equiv
alent situation occurs in the flow between two parallel plates driven by the
motion parallel to the plates. This case is known as plane Couette flow. It is
equivalent to the motionof coaxial cylinders withradii muchlarger thanthe gap
between the cylinders, and the curvature effect is neglected.
Secondary flows (closed vortices), observed in the flow of a “rheological’ liquid
in a gap between a cone and a plate when a cone is rotated around its axis, are
shown in Figure 4.16b.
84 Rheological equations of state
If a liquid is forced to flowthrough a straight channel with an elliptical or rect
angular crosssection in the direction of the main flow along the axis of a chan
nel, the secondary flow forms closed flow lines in the crosssection of a channel
(Figure 4.16c). The most spectacular secondary flow, in the form of closed vorti
ces, occurs in a “rheological” liquid flow through a sudden narrowing (Figure
4.16d).
Instability of the Taylor vortices is explained for regular Newtonian liquids as
a result of inertial effects (analogous to the Reynolds turbulence). Taylor insta
bility occurs in any Newtonian liquid if a critical value of the Reynolds Number
is exceeded. Theoretical analysis of the flow of a Newtonian liquid shows that
the stability threshold for flow between two coaxial cylinders is determined by
the value of the Taylor Number, T, calculated as
A. Ya. Malkin 85
Figure 4.16. Secondary flows in different channels: between two rotating coaxial cylinders (a),
along a nonround element (b), in channel crosssection (c), near a sudden change of crosssection
surface area (d).
T =2b(Re)
2
ε [4.18]
where
b=
o i
i
Ω Ω
Ω
−
Ω
i
andΩ
o
are the rates of rotation of the inner and outer cylinders, respectively;
if Ω
o
= 0, b = 1, ε δ = R
i
is the ratio of the gap to the radius of the inner cylinder
and
Re =
R
i i
Ω δρ
η
[4.19]
is the Reynolds Number determined for a circular flow between coaxial cylin
ders.
The height of the Taylor cells formed in a Newtonian liquid in a section along
the axis of cylinders is roughly equal to the width of a gap, i.e., the formof cells is
close to square.
One of the main theoretical findings for a Newtonian liquid is the existence of
the minimal value of the critical Taylor Number equal to 3390 (at b = 1).
Elasticity of “rheological” liquids strongly influences the stability of flow. Ex
periments show that elasticity (for example, characterized by the normal
stresses) can stabilize the Couette flow. Besides, some investigators observe
newtypes of instability in the Couette flow; for example, wavy cells with bound
aries periodically changing with time.
20
Appearance of cells of different type, as
documented, depends on rheological properties of a liquid.
Instabilities observed in highly elastic (rubbery) liquids are quite different
than those described for Newtonian or weakly elastic liquids. Firstly, instability
occurs irrespective of the Taylor Number (for example, it can happen even at T
close to zero, quite analogous to instability of the melt fracture type which also
appears irrespective of the Reynolds Number and even at Re close to zero). Sec
ondly, cells can be of very irregular form, reminding us of rough extrudate dis
turbances in capillary flow. Thirdly, it is possible to observe instability of the
oscillatory type, again reminding us of periodic distortions of an extrudate.
86 Rheological equations of state
Instability related to a secondary flow also can be observed in other circular
(rotational) devices, as is shown in Figure 4.16b. The coneandplate system is
very often used in experimental rheology for viscosity and normal stress mea
surement, and in this case the angle between a cone and a plate does not exceed
4  5
o
.
Inertial instability in a form of closed vortices appears in circular flow of a
Newtonian liquid between a cone and a plate at sufficiently high values of the
Reynolds Number. In circular flow of a “rheological” liquid, instability begins
from distortion of a meniscus due to elastic effects. These distortions can be
rather extensive.
More severe effects cause a rupture of a liquid sheared between a cone and a
plate. It does not happenimmediately after the beginning of rotation, but after a
periodof deformation. This effect also canbe consideredas analogous to flowdis
turbances and melt fracture of an extrudate leaving a die.
Avery important type of secondary flowoccurs whenthere is a suddennarrow
ing in axisymmetrical geometry of a channel (Figure 4.16d). This situation is
typical in a transition from one diameter of a pipe to a smaller diameter; for ex
ample, in liquid transportation or in a die in industrial extruders or capillary
viscometers.
Many visual experiments demonstrated that vortices appear at the corners, as
showninFig. 4.17. Experiments proved that the shape and behavior of suchvor
tices are characteristic for properties of a “rheological” liquid. However, in a typ
ical case, at lowflowrate, the stable vortices exist at the corners. Increasing the
rate of flow (equivalent to the increase in the Weissenberg Number), regular
pulsation of vortices occurs. Further increase in flow rate causes pulsations to
become irregular. It is interesting to emphasize that these transitions in behav
ior of vortices correspond to the character of flow inside a die and distortions of
an extrudate. Thus the observations regard the transition from typical second
ary flow to a chaotic instability of turbulent type.
Another interesting feature of flow through sudden decrease in crosssection
surface area is axial extensionof a liquid near the axis of a stream. Withincreas
ing flow rate, the draw ratio increases, creating a combination of instability of
secondary and extensional flow. In particular, when a rate of extension exceeds
some threshold value, fracture of flowlines is observable along the axis, i.e., flow
ruptures in a continuum media. This phenomenon is a limiting case of instabil
ity in extensional flow. It superimposes on vortex formation, and a result of
A. Ya. Malkin 87
these effects leads to extrudate distortion and melt fracture, with all the techno
logical significance of these effects for processing of viscoelastic materials, as
mentioned before.
Insummary, inshear curvilinear flows, for example, ingaps betweentwo coax
ial cylinders, a cone and a plate, in threedimensional flows in sudden change of
crosssection, instabilities of different types occur. The first type is related to
normal stress influencing critical conditions responsible for secondary flows,
88 Rheological equations of state
Figure 4.17. Photograph illustrating the appearance of closed vortices near a sharp corner around
a sudden reduction of crosssection surface area.
causing formation of regular vortices (this is a weak nonlinear effect). In this
case, the secondary flowappears as a chaotic movement of particles ina liquid or
irregular distortion of smooth surfaces of a stream. The second type causes se
vere distortion of a media in oscillatorytype movement (this can be treated as a
strong nonlinear effect). The irregular instability which occurs as a result of
ruptures in a continuum media can be considered as a result of phase (or
relaxational) transitions, and can be treated as a “phase” nonlinear effect. The
effect close to it is a phase separation which occurs due to shearing,
21
observed in
mixtures and solutions.
4.1.6.3 Waving in Extensional Flows
There are very interesting and unusual effects observed during stretching of
“rheological” liquids. These effects are important in many technological pro
cesses, such as the commercial process of fiber spinning and orientation, where
the natural tendency to increase the process rate is contrary to the requirements
to prevent process instability caused by “fast” flow.
In practice, the following phenomena are met which can cause instabilities of
different type.
Drawresonance is a wavy periodic change in stream (fiber) diameter occur
ring at constant feed (takeup) rate.
22
It is impossible to avoid occasional small
fluctuations in fiber diameter, but instability is the phenomenon which in
creases these fluctuations. It is reasonable to assume that drawresonance is due
to elastic behavior of a liquid, and this phenomenon can be described in terms of
nonNewtonianbehavior inuniaxial extension, thus the DeborahNumber is the
determining parameter for this phenomenon. Drawresonance affects quality of
fibers (expected to have uniform crosssection).
Jet breaking occurs in a Newtonian liquid due to surface tension (capillary
waves break up a stream, as explained in the classical works by Rayleigh).
23
The
reasonfor jet breaking is a growthof small occasional wavy variations ina diam
eter of a jet until a cylindrical jet breaks up into droplets.
24
The main difference
between a regular and “rheological” liquid is in the formof a jet before breakup.
As mentioned in discussion of extensional flowof “rheological” liquids, a stream
is initially converted to a series of elongated droplets connected by threads.
These threads can be stretched at a rather large ratio (especially if the resis
tance to stretching increases on drawing), leading to stream stabilization. That
is why “rheological” liquids, for example, very diluted water solutions of some
A. Ya. Malkin 89
polymeric substances, can be successfully used in fire extinguishing when it is
desirable to prevent jet breaking andto increase the distance of streamdelivery.
Necking was already mentioned in discussion of uniaxial tension of solid
viscoelastic materials. It is anabrupt deviationfromuniform(homogeneous) de
formation.
25
It is an instability of the phase type, consisting of selfsustaining
change in the diameter of a stretched filament. This effect is typical for large de
formations of solid materials. It is related to relaxation or phase
(recrystallization) phenomena. It also occurs during extension of liquids (poly
mer melts). Necking is very important in such technological operations as orien
tation of amorphous materials and orientational crystallization in fiber
spinning.
Rupture of a stream, observed in uniaxial extensional flows, is the final stage
of instabilities. It can happen as a result of development of surface waviness in
draw resonance or jet breakup (surface instability) or as a result of cohesive
fracture even though it is encountered in liquids. It is important to mention that
this cohesive fracture occurs at the same magnitude of stress as in melt fracture
of an extrudate leaving a die. It emphasizes the correlation between the
strength (rupture) of a material and major distortion observed in concentrated
solutions of polymers and melts.
4.1.6.4 Interfacial and Surface Instability
In coating processes, shear flows of films with a free surface are observed. A
technologist expects that a liquid film on a solid base should be smooth and ho
mogeneous  not always the case because of surface instabilities in a flow of a
coating liquid.
26
It is important in surface coating, especially in automotive ap
plication where anticorrosive coatings are used.
The model of such a situation is a flowof a liquid filmalong an inclined plate. A
stream with a free surface can become unstable, as demonstrated by imperfec
tions of a free surface. An analogous phenomenon is observed in
multicomponent flow through channels. Waves are formed at the boundaries of
two liquids.
Interfacial and surface instabilities occur for Newtonian liquids due to inertial
effects. The stability of flow is controlled by the Reynolds Number and the sur
face tension. The influence of the Weissenberg Number, controlling surface in
stability, is an additional factor typical of “rheological” liquids. Theory predicts
90 Rheological equations of state
that elasticity of liquid, even at very low values of the Reynolds Number, can
lead to waviness of a surface, which is a purely rheological effect.
4.1.6.5 Rheological Phenomenon in Inertial Turbulence (Toms Effect)
Inertial turbulence exists in “rheological” liquids similar to many other effects
of instability discussed above. Also in this case, special properties of some “rheo
logical” liquids lead to a very abnormal (compared with regular liquids) phe
nomenon known as the Toms effect.
27
It is a very interesting, unusual, and
important phenomenon worthy of separate discussion.
In order to understand the meaning of the Toms effect, it is necessary to repeat
some fundamental concepts of classical hydrodynamics of viscous (Newtonian)
liquids.
It is wellknown (see also Chapter 5) that pressure drops during the flowof vis
cous liquid through a cylindrical tube (capillary, channel), i.e., the difference of
hydrostatic pressures at the ends of a tube, ∆P, is related to the volumetric flow
rate, Q. If and until the flowrate is not very high, the relationship betweenthese
two main macrocharacteristics of a stream is expressed by the Hagen 
Poiseuille equation,
28
which can be written as follows
∆P=
128 LQ
D
4
η
π
[4.20]
where D is a diameter of a tube, L length, η viscosity. Alternative form of
Eq 4.20, when substituting the volumetric flowrate by an average velocity, V, is
as follows:
Q=
1
4
D V
2
π
Then we have
∆P=
32 LV
D
2
η
[4.21]
Finally, let us introduce dimensionless characteristics of flow, i.e., the
Reynolds Number, defined in Eq 4.14, with V in this formula being an average
A. Ya. Malkin 91
velocity. The second dimensionless number is a coefficient of friction, λ, which is
determined as
λ
ρ
=
P
1
2
V
D
L
2
∆
[4.22]
Now, the Hagen Poiseuille equationcanbe writtenwithdimensional variables
λ =
64
Re
[4.23]
Sometimes bothnumbersλ andRe are determined, not throughdiameter, D, but
by radius, R, of a tube, then
Re =
VR
; =
P
1
2
V
R
L
R R
2
ρ
η
λ
ρ
∆
So the Hagen  Poiseuille equation looks like this:
λ
R
R
=
16
Re
Changing D for R does not influence the result, and both dimensionless forms
are equivalent to the initial Eq 4.20. Application of dimensionless Numbers λ
and Re is of general meaning for hydrodynamics flow through tubes, because
such an approach allows one to generalize data for different liquids and tubes of
various geometrical sizes (diameter and length) by representing them in
dimensionless coordinates λ and Re in one relationship. It is generally accepted
to analyze the pressure versus output (flow rate) relationship in terms of λ and
Re for any flow velocity, not only when Eq 4.20 is fulfilled.
It is well knownthat the Hagen Poiseuille equationcorresponds to the experi
mental data only upto some critical value of the Reynolds Number, Re*, whichis
close to 2300 (i.e., log Re* = 3.36). Increasing flow rate (or the Reynolds Num
92 Rheological equations of state
ber), the transient regime is attained, which lies in the range of Re* to Re**, and
at Re >Re**, turbulent flow occurs.
The dependence of the friction coefficient on the Reynolds Number, for a fully
developedturbulent regime of flow, inthe range of the Re values upto 10
5
, is well
described by the empirical Blazius equation
29
λ =
0.3164
Re
0.25
[4.24]
The generalized λ(Re) dependence, established on the basis of numerous re
search experiments covering all regimes of flow, is drawn in Figure 4.18. In this
graph, constructed in log  log coordinates, the line P corresponds to the Hagen 
Poiseuille equation, and the line B is drawn according to the Blazius equation.
Evidently, the transition from laminar to turbulent flow results in a great in
crease of resistance to flow, with corresponding increase of energy due to the
movement of a liquid. The critical values of the Reynolds Numbers Re* and Re**
are also marked in Figure 4.18.
A. Ya. Malkin 93
Figure 4.18. General view of the dependence of friction coefficient on the Reynolds Number.
t regular (Newtonian) liquid,  “rheological” liquid, P Hagen  Poiseuille equation, B Blazius
equation, V  Virk asymptote.
The Toms effect in “rheological” liquids describes the decrease in resistance to
flow (drag reduction) in adding very small amounts of some components to a
regular liquid (the latter can be, for example, water or oil). These special addi
tives are, as a rule, polymers of very high molecular weight (with very long flexi
ble chain) and their concentration in solution can be as small as 1  100 ppm
(parts of anadditive per 1 millionparts of a liquid). These microquantities of ad
ditives are the reason for the appearance of new rheological properties of mat
ter.
The effect appears from some threshold value of Re, marked in Figure 4.18 as
Re*. Black points in Figure 4.18 correspond to a pure liquid (solvent) and the
light points to “rheological” liquid (very dilute polymer solution). In the laminar
and transitional ranges, both sets of points fall into the same dependence. The
same is true at the beginning of a turbulent regime of flow, but at Re > Re* the
situation changes radically and a coefficient of friction for a “rheological” liquid
becomes lower than for regular liquid.
Many publications have been devoted to the Toms effect. The main results
about general peculiarities of the Toms effect are:
• the value of Re* decreases on increase of solution concentration; in the limit
ing case, Re* can become as lowas Re**, and the transient regime of flowbe
tween Re* and Re** disappears
• the degree of drag reduction depends on the material properties (type of liq
uid and an additive, concentration of a solution, and so on), i.e., the effect de
pends on rheological properties of a liquid
• there is a limiting (asymptotic) degree of drag reduction in polymer solu
tions, common for all materials; it can be represented by dimensionless vari
ables as described by the equation called the Virk asymptote:
30
λ = 2.36Re
0.58
[4.25]
The Virk asymptote is draw in Figure 4.18 under the symbol V.
Comparison of graphs Band Vin Figure 4.18 shows that the maximal effect of
drag reduction can reach 75%. Certainly, it is a very strong effect, and as such, it
finds practical applications in liquid transportation. Also, special additives are
used as a smoothing agents of fast movement of ships when turbulence requires
additional energy use. The additives, by decreasing resistance, promote attain
ing higher speeds at the same engine power.
94 Rheological equations of state
4.1.7 THIXOTROPY AND RHEOPEXY
Very often, real materials change their properties with time due to the struc
ture transformations resulting from an action of external forces or rebuilding
their initial structure at rest. The reason for change can be a preliminary defor
mation: in this case, rheological properties (in the simplest case  viscosity)
change along with deformation and continue to change at rest after cessation of
deformation. Such phenomena do not exist in Newtonian liquids having con
stant viscosity.
The change of properties can be fully reversible, though it may require a long
time or even special actions (for example increase of temperature to accelerate
processes during the material’s rest). Some changes initiated by deformation
can be stored in a material and then recovery may be incomplete. Both cases are
real and observed; for example, in yogurt on mixing, in preparation of rubber
compounds, shearing of thickened greases, pouring building materials, and so
on.
If viscosity decreases during mixing andreturns to the initial level onrest after
shearing, such a phenomenon is called thixotropy.
31
The reverse phenomenon
is called rheopexy. The definitions of
thixotropy and rheopexy are valid not
only for regimes of steady flowbut also for
transient deformations. The use of these
terms is not always very definite, and
thixotropic and rheopectic effects are fre
quently mixed with other viscoelastic ef
fects.
A typical example of thixotropic behav
ior of liquid is given in Figure 4.18, show
ing the relationship of viscosity versus
shear rate. The upper part of a curve was
measured on increasing shear rate; on re
verse measurement (shear rate decreas
ing from maximum to minimum),
viscosity is lower thanonascending shear
rate change. The lower part of the curve
represents viscosity of a medium with
A. Ya. Malkin 95
Figure 4.19. Hysteresis loop in continu
ous change of shear rate formed due to
thixotropic properties of a liquid. An ar
rowshows the direction of changes of ex
perimental conditions in viscosity
measurement.
structure changed by previous deformation. Measurements are used to charac
terize thixotropic properties of material and their quantitative measure is an
area of a hysteresis loop between two curves in Figure 4.19.
Structural effects in highly filled liquids can lead to a very peculiar rheological
phenomenon called dilatancy, which is volume increase caused by shear. De
formation of moist sand or concrete are typical examples of dilatancy. Mixture
becomes dry under pressure but recovers and becomes moist after the pressure
is removed.
32
Solid particles in such materials are in a state of close packing. Un
der shear, particles must be separated and liquid acts as a lubricant. Particle
coating by liquid increases volume.
33
The change of rheological properties ondeformationand rest reflects the struc
tural rearrangement caused by application of external forces. In this sense,
thixotropy is a consequence of structure rupture and rheopexy of structure
buildup. It can be expected that external forces more likely promote rupture
rather than a buildup of structure, and that is why thixotropic effects are more
common than rheopexy, the latter being a very special case in materials with
some kind of unusual intermolecular interactions; for example, strong ionic in
teraction or hydrogen bonding.
It is important to emphasize that in both cases, a new class of phenomena is
discussed within the frame of rheology, that is, kinetics of physical or chemical
processes in a material related to the effect of stress. Kinetic effects in rheologi
cal systems can be called rheokinetics or chemorheology.
There are two main cases of chemorheological effects. One of them is a change
of stresses (relaxation) in deformed materials as a result of chemical reaction
initiated by stress. This phenomenon is particularly important for rubbers, as
was investigated in fundamental works by Tobolsky.
34
The second case regards
chemical reactions of polymerization, curing of oligomers, and chemical trans
formations inpolymeric chains.
35
All these chemical reactions result inconsider
able changes of rheological properties (not only viscosity) of a material.
Certainly this type of phenomena is especially important in applications of poly
mer technology (synthesis and processing).
Changes in the matter structure are followed by changes in its properties.
They lead to new values of parameters characterizing these properties; for ex
ample, viscosity of a liquid or modulus of elasticity of a solid. The set of these pa
rameters differs for any actual state of a material structure. Results also depend
on the conditions of measurements of these properties. Fromthis description, it
96 Rheological equations of state
is apparent that the behavior of material is nonlinear, and the effects are
caused by transformations of a physical structure of matter. That is why rheo
logical effects related to structural transformations of a material can be called
physical nonlinearity of rheological behavior. In discussion of nonNewto
nian flow, it already has been mentioned that the idea of physical nonlinearity,
as a reason for this effect, was introduced by Ostwald
1
under the name of struc
ture viscosity. A similar reason can lead to other rheological effects.
4.1.8 NONLINEAR ELASTICITY
According to the Hooke Lawthe dependence of elastic deformations onstress is
linear and the modulus of elasticity (the ratio of stress and deformation) is a ma
terial constant. This idea looks quite natural because any complicated function,
such as σ ε = f( ), can be expanded into a power series. The first (linear) member
will always be dominating, because at ε << 1 and at n > 1, the ε ε
n
<< . Thus,
higher members of the series are negligible in comparison with the linear mem
bers.
Sometimes large elastic deformations are treated as a secondorder effect. If
one expands the functionσ ε = f( ) into a power series, thenthe term“large elastic
deformations” means that the second (quadratic) member of a series becomes
comparable to the linear member. Whenε << 1, the quadratic member is negligi
ble, but as ε approaches 1 and exceeds it, then the “secondorder” effect becomes
dominant.
Even for some ordinary materials, at rather lowdeformations, the Hooke Law
appears not exactly true, the dependence σ ε ( ) is nonlinear and, as demon
strated by Bernoulli, approximately at the same time when Hooke formulated
his Law, properties of some materials are better described by power law:
σ ε
E
m
= K
where K and m are empirical constants (m is not equal to 1).
It is worth mentioning that Bernoulli conducted his experiments with biologi
cal materials whichare rather complicated intheir structure, while Hooke dealt
with rather simple homogeneous materials.
The properties become more complex for materials which can withstand large
deformations (ε > 1). This is a case especially important for rubbers, some poly
mer solutions, and colloid systems (for example, dispersions of aluminum
A. Ya. Malkin 97
naphthenates). Drawratio, λ, for these materials can reach values of an order of
10 and even more. In such cases, the nonlinearity of stress versus deformation
dependence is evident as a typical rheological effect.
There are some popular equations for describing dependence of draw ratio on
the stress of rubbers. The most often used formula, the socalled
KuhnGuthMark equation,
36,37
can be written (for uniaxial extension) as
σ λ λ
E
2 1
= G ( )
∞
− [4.26]
where G
∞
is an equilibrium modulus, and λ draw ratio.
Sometimes “conventional” stress, σ
o
, (drawing force divided by initial
crosssection of a sample) is used instead of the true stress, σ, (force divided by a
current crosssection of a sample, taking into account changes of the crosssec
tion along drawing). If the volume of a sample does not change during deforma
tion (very close to reality for rubbers), the relationship between conventional
and true stresses is very simple
σ σ λ
o E
=
and Eq 4.26 takes the following form
σ λ λ
o
2
= G ( )
∞
− [4.27]
It is easy to show that within the limit of small deformations (at draw ratio
λ ε → 1or <<1), Eq 4.26 becomes
σ ε
E
= 3G
∞
[4.28]
It means that, within the limit of small deformations, the Hooke Law is valid,
and the Young modulus equals 3G
∞
.
The divergence fromlinearity of σ ε ( ) dependence, predicted by Eq 4.26, is illus
trated in Figure 4.20. It is quite evident that nonlinear effects appear at rather
large deformations. Initial slope of the curve (dotted line in Figure 4.20) equals
3(λ  1), corresponding to Eq 4.28.
It is important to emphasize that Eq 4.26 is a singleconstant equation (con
tains only one parameter G
∞
). Another singleconstant equation for large defor
98 Rheological equations of state
mation was proposed by Bartenev and
Khazanovitch.
38
For uniaxial extension it
has the following form
σ λ λ
E
1 2
= A( ) −
where A is an empirical constant.
Numerous other equations for large defor
mations, discussed in scientific literature
and used in practice, are multiparametric.
Among them is the Mooney  Rivlin equa
tion,
39
which is the most popular equation.
For uniaxial extension, this equation is writ
ten in the following form
σ λ λ λ λ
E 1
2 1
2
2
= 2[C ( ) + C ( )] − − [4.29]
where C
1
and C
2
are empirical <%5>con
stants (parameters).
Quite different twoparameter equation of
power type, for large deformations, was pro
posed.
40
For uniaxial extension it has the fol
lowing form:
σ λ λ
E
n
\n 2
= 2B( \ ) [4.30]
where B and n are empirical constants. Eq 4.30 is close to the equation earlier
discussed by Ogden
41
and can be treated as an analogue to the power law for
nonNewtonian liquids (Eq 4.5).
Certainly, experimental data on uniaxial extension at large deformations (like
any other set of experimental data) can be described in many different ways by
means of equations of various mathematical structure. It seems that there is
only one formal limitation: existence of a linear regioninthe limit of small defor
mations. There are some other inevitable limitations for use of arbitrary stress
versus deformation equations and they will be discussed below on the basis of
general principles for constructing rheological equations of state. That is why
A. Ya. Malkin 99
Figure 4.20. Stress versus deforma
tion dependence predicted by the
KuhnGuthMark equation. Dotted
line is linear stress versus deforma
tion dependence.
other possibilities for describing large deformation will be discussed below
within the frame of a general theory of elastic bodies (Chapter 6).
Large elastic deformations lead to numerous macroeffects and they can be a
source of some effects whichmight be treated as independent rheological effects;
for example, large elastic deformations during shear are intimately related to
the Weissenberg effect, and perhaps, at least in some cases, they correspond to
nonNewtonian flow of “elastic” (i.e., capable of superposition of flow and recov
erable deformations) liquids.
There are some direct consequences of large elastic deformations in different
media. For solids, it includes the socalled Poynting effect.
42
It consists of ex
tension of a body when sheared. It leads to an increase of its length, even though
in a classical Hookean solid the deformation of one type (twisting) must not in
fluence deformationof another (longitudinal extension). It is interesting to men
tion that, according to original experimental data, axial deformations observed
in the Poynting effect are proportional to the squared angle of twisting. That is
why the Poynting effect and some other related manifestations of large elastic
deformations are sometimes called effects of the second order.
An increase of a diameter (swelling) of liquid streams is another manifestation
of large elastic deformations. When an elastic liquid leaves a capillary (or a die),
its diameter increases above a diameter of a channel, though a diameter of
stream in flow of classic Newtonian liquid must decrease. The origin of this ef
fect, called die swellingor the Barus effect,
43
is also related to large elastic de
formations developed during the flow through a channel.
44
Large elastic deformations can act in combination with other rheological ef
fects. One of the most interesting cases includes superposition of large elastic
deformations and thixotropy, when large deformations destroy the inherent
structure of a material. This situation is typical, for example, for filled rubbers
(rubbers containing reinforcing filler such as carbon black) or crystalline solid
plastics. In this case, repeated deformations (stretching  compression cycle or
periodic large amplitude shearing) lead to change of observed stress versus de
formation dependence which approach some “equilibrium” shape only after sev
eral loadingunloading cycles. The phenomenonis calledthe Mullins effect.
45
Indiscussionof the theory of deformations (Chapter 3), it was shownthat some
nonlinear effects may occur purely for geometrical reasons and can be ex
plained and described if we want to use “correct” (or corrected) measures of the
effect. For example, introduction of Hencky’s measure of deformations allows
100 Rheological equations of state
one to “linearize” the behavior of a material because deformations are summa
rized in accordance with a linear rule. That is why corresponding phenomena,
whichare only due to geometrical transformations of a body and canbe excluded
by introducing “proper” quantitative measures of an effect, can be treated as
geometrical nonlinearity in rheological behavior.
4.1.9 VISCOELASTIC BEHAVIOR
(TIME EFFECTS AND SUPERPOSITION OF FLOW AND ELASTIC DEFORMATIONS)
Superposition of viscous and elastic behavior is a typical and important rheo
logical effect characteristic of real materials. This phenomenon is called
viscoelasticity. It canbe observed indeformationof all materials, evensuchas
metals and stones, on the one hand, and water and oil, on the other. The differ
ence is only in the relative participation of elastic and plastic components and
the sensitivity of the method used for their investigation.
The idea of viscoelasticity of solids was introduced into scientific discussions
by Lord Kelvin (W. Thomson), who applied this concept to deformation of the
Earth.
46
Longterm, very slow deformations of metals under stress, damping of
vibrations of bells, and many other phenomena of this type are all consequences
of viscoelastic properties of real materials.
47
However, the most important class
of materials possessing viscoelastic properties include polymers (rubbers, plas
tics, solutions) because viscoelastic phenomena are observed in deformations of
these materials in ordinary timescale (seconds, minutes, and hours), while ob
servation of viscoelastic effects for other materials requires either very short
(fraction of a second) or very long (years) timescales.
There are two mainphenomena related to viscoelastic properties of a material.
They are creep and relaxation, though viscoelastic behavior of a material can
be observed in numerous other experiments and applied situations.
Creep is slowdevelopment of deformations at a constant stress. For a Hookean
elastic body, application of a constant stress creates constant deformation,
which appears (practically) instantaneously and does not change as long as
stress continues to be constant. For a Newtonian liquid, application of constant
stress leads to flow with a constant rate of deformation. The behavior, called
creep, is illustrated in Figure 4.21. We can distinguish three different cases:
• limited creep  deformation reaches its maximum level and after that does
not change; this behavior reflects viscoelastic properties of solids
A. Ya. Malkin 101
• limited rate of deformation  after a transient period, constant rate of defor
mation is set. This constant value of deformation rate is given by the curve 2,
the behavior reflects viscoelastic properties of liquids which flow at con
stant rate of deformation
• accelerated creep  not only deformation but also the rate of deformation
show limitless increase until the rupture of a body; this situation is typical
for both liquids and solids, if stresses are sufficiently high and exceed cohe
sive strength of material.
In the first case shown in Figure 4.21,
full deformation is completely elastic (or
reversible). It means that, if an external
force is removed, the initial dimensions of
a body are completely restored. In two
other cases, full deformation consists of
elastic (reversible) and plastic (irrevers
ible) components. It means that after re
moval of an external force, the initial
dimensions of a body are only partially be
restored. This difference is demonstrated
in Figure 4.22, which can be treated as a
continuation of first two curves in Figure
4.21. The portions of curves, after the dot
ted line xx, reflect behavior of a material
after removal of an external force; the re
sulting deformation is zero in the first
case and there is a residual deformation,
ε
f
, in the second case (the third case in
Figure 4.21 gives similar picture as the
second case).
Creep is an important property of many materials which are not very “rigid”
or/and fragile. Creep is practically nonexisting in metals at room temperature
but it becomes a very serious problemif a metal is used close to its melting tem
perature, as characteristic, for example, for hightemperature steels used in gas
turbines. Creep is also important for parts working under high stresses for a
long time, for example, pipes under internal pressure. Creep is of special impor
tance in different types of plastics, including reinforced plastics, highly filled
102 Rheological equations of state
Figure 4.21. Different types of creep: lim
ited deformation (curve 1), limited con
stant rate of deformation  marked at the
curve (curve 2), and accelerated creep
(curve 3).
polymers (for example, solid
propellants), because they are
usedat temperatures not far be
low their melting temperature.
That is why measurement of
creep is very popular inpolymer
material science.
Relaxation is a slow decay of
stresses at constant deforma
tion. For a Hookeanbody, stress
continues to remain constant
during preservationof deforma
tion. For a Newtonian liquid,
stress cannot act if rate of defor
mation is absent (it is absent at
constant deformation, because
the derivative of a constant is zero). In real bod
ies, stress decay is not instantaneous but re
quires time as shown in Figure 4.23. One can
distinguish two possible situations, as illus
trated in Figure 4.23:
• stress may dissipate and completely disap
pear  this is a case of stress relaxation in a
viscoelastic liquid
• part of an initial stress, σ
∞
, can be stored in a
material for unlimited time, in the case of a
viscoelastic solid.
Both basic viscoelastic phenomena can be con
sideredas a mutual delay inchange of stress and
deformation. Thus, it is necessary to introduce
time as a factor determining the stress versus
deformation relationship and accept that an unambiguous correlation between
stress and deformation does not exist.
In fact, the concept of relaxation is much wider than only slow decay of
stresses. Maxwell, who introduced an idea of relaxation in physics,
48
used this
term to designate delayed restoration of a molecular structure of matter dis
A. Ya. Malkin 103
Figure 4.22. Elastic recovery of deformation after re
moval of stress for a viscoelastic solid body with re
sidual deformation, ε
f
, (curve 1) and viscoelastic
liquid (curve 2).
Figure 4.23. Relaxation in
viscoelastic liquids (curve 1)
and solids (curve 2). Residual
stress equals σ
∞
.
torted by any external factor or (maybe) simply by a statistical fluctuation. Then
we can understand relaxation as restoration of an equilibrium state, disturbed
for any reason.
Any time effect is a consequence of various transformations of inherent struc
ture of a material and kinetic processes of this restoration. In this line of
thought, the viscoelastic behavior can be treated as a thixotropic effect of some
kind. At least in some cases, both phenomena are intimately related to each
other. However, as a general rule, viscoelasticity is considered as an independ
ent phenomenon and the theory of this effect (Chapter 7 is devoted to the com
plete discussionof this theory) is constructed regardless of analysis of structural
and/or kinetic processes which may take place in a body.
In practical applications, relaxation is always considered when a material or a
structure as a whole is deformed. A rather obvious example of relaxation is of
fered by damping of vibrations by shockabsorbers in cars and other transport
devices. Exploitation of seals in pressure vessels is another example. In initial
state, seals can be very tightly pressed by screws. The relative positions of a
cover and a vessel are not changed during work (i.e., deformation of a seal con
tinues to be constant) but due to relaxation; a material becomes unstressed and
sealing becomes not as tight as it was in the beginning.
4.1.10 FLOW AROUND SOLID OBSTACLES
Flowof liquidarounda solidbody (obstacle) is aninteresting andimportant ex
ample from hydrodynamics. The effect is the same when a stream flows around
a solid body or a body moves through a liquid medium, similar to river flow un
der the bridge or a ship moving ina sea. Inbothsituations, the hydrodynamic re
sistance to movement is of interest.
Classical experimental and theoretical investigations (initiated by A. Eiffel in
the 19th century) showed that the general hydrodynamic picture can be demon
strated as in Figure 4.24, and there are two characteristic effects observed:
• existence of a point at which a streamis diverted by a body, and this point is
characterized by the value of an azimuthal angle, β*
• formation of vortices after passing the point of first contact between a body
anda stream; they appear eveninlaminar flowandremainstable after pass
ing a solid body in the form of socalled Karman’s strip.
These effects are observed in flow around any solid body with smooth curva
ture (spheres, cylinders, ovals, and so on). It is worthmentioning that the hydro
104 Rheological equations of state
dynamic resistance in all
cases is primarily determined
by the pressure of a streambe
fore the point of contact, and
contributionof viscous friction
does not exceed 2%of the total
resistance. Heat and mass ex
change processes between a
liquid and a solid body during
these process is of special sig
nificance in the design of heat
exchange equipment.
It is important to emphasize that the value of the azimuthal angle, β*, found in
flow of numerous Newtonian liquids is rather constant and close to 82
o
in the
range of the Reynolds Number from3×10
2
to 3×10
5
. This range covers the transi
tion zone from laminar to turbulent flow, typical of real technological applica
tion.
Experiments and some theoretical studies showed that the azimuthal angle,
β*, is lower than 82
o
for nonNewtonian liquids. A more pronounced effect is ob
served if liquid is not purely viscous but also has elastic properties (for example,
polymer solutions, some biological liquids, etc.). The following new effects are
observed here: the position of the point of stream diversion becomes variable
and moves upstream. The shift can be so large that β* reaches 180
o
and flow ap
proaches an undisturbed pattern flowing around a body in the range of the
Reynolds Numbers mentioned above.
This is a consequence of rheological properties of a medium, namely, elasticity
of a liquid. This effect is frequently used in technology where liquids are modi
fied to impart elastic properties.
4.1.11 PHASE TRANSITIONS INDUCED BY DEFORMATIONS
Deformations of some materials can lead to phase (or at least to relaxation)
transition under isothermal conditions. Treating this phenomenon as a rheolog
ical effect (though one may think that there is some conditionality in such treat
ment) has the following reasons:
• it happens withmaterials whichmanifest many other rheological effects dis
cussed above
A. Ya. Malkin 105
Figure 4.24. The picture observed when a liquid flows
around a solid body at transient range of the Reynolds
Numbers between laminar and turbulent regions.
• it leads to a very strong change in rheological properties of matter during its
deformation
• at least in some cases, several rheological effects discussed above can be ex
plained based on the idea of phase or relaxational transition occurring as a
consequence of deformation.
There are some very typical and practically important situations observed in
deformation of polymer solutions and melts related to transitions caused by de
formations and therefore treated as rheological effects. They are:
• necking  formation of a sharp contraction in uniaxial stretching of many
amorphous and crystalline polymers at some critical deformation; further
stretching occurs through transition of an initial width into a uniform nar
row “neck”
• orientational dewetting (or phase separation)  at very high rates of ex
tensionof some polymer solutions, polymer becomes insoluble (it means that
transition into a twophase system takes place) and polymer precipitates
from solution; similar effects were observed in shear when phase transition
shifted along the temperature scale on increase in shear rate
• spurt in flow at high stresses, polymer, moving along a channel, loses its
fluidity and begins to slip froma solid wall of a channel. This phenomenon is
caused by flowtorubbery state transition
• orientational crystallization deformationcanshift temperature of equi
librium crystallization and thus it influences kinetics of isothermal phase
transition; this effect is well known in stressed rubbers. Crystallization un
der deformation in loaded parts radically changes their mechanical proper
ties and can lead to an unexpected breakage during operation.
Phase and relaxational transitions caused by deformations lead to very sharp
changes in rheological properties of a material. That is why effects related to
transitions can be classified as phase nonlinearity in rheological behavior.
4.2 GENERAL PRINCIPLES
Formulation of rheological equation of state requires answers to the following
questions:
• rheological effects are observed (as a rule) in rather simple unidimensional
deformations  how to describe them in threedimensional space?
• many different effects coexist  can they be considered as independent or are
at least some of them a consequence of the same inherent mechanism?
106 Rheological equations of state
• rheological properties of a material are measured under some chosen condi
tions  is it possible to predict behavior of a material in other situations?
What is the minimal range of experiments necessary to make a valid predic
tion for a full set of different stress states?
• are the empirical methods, used to generalize different experimental re
sults, not contradictive?
Let us assume that sets of experimental data were obtained for different condi
tions of deformation; for example, in uniaxial extension and simple shear. Each
such set of data can be described by an empirical equation. The final interpreta
tion would be simple if both observed cases of rheological behavior of the same
material would not offer two different manifestations of inherent properties of
matter. Then both stress versus deformation equations must be considered as
consequences of a general rheological equation of state of a material. In other
words, equations for different geometrical modes of deformation must be com
patible.
There are some general limitations for rheological equations of state to pro
duce compatible stress versus deformation relationships for different geometri
cal modes of deformation. The limitations will be discussed below, whereas
rheological equations of state for main groups (types) of materials will be ana
lyzed in Chapters 5 and 6. In particular, it will be demonstrated that stress ver
sus deformation (or rate of deformation) equations written above can be treated
as consequences of some general rheological equations of state. Moreover, the
same equations for onedimensional deformation can be obtained fromquite dif
ferent rheological equations of state, i.e., the same experimental data can be
generalizedina different way. These different equations of state give nonequiv
alent predictions for other deformation modes. That is why, in order to establish
the correctness of the equationof state, it is necessary to have experimental data
from several different geometrical modes of deformation.
Let us discuss characteristic and important cases, illustrating the above prob
lemin regard to properties of anisotropic materials. It has been known for years
that mechanical properties of even such old and popular material as cast iron
are different in extension and compression. This means that it is incorrect to
predict behavior of this material in engineering application based on results of
measurement of its properties in extension if material actually works in com
pression mode.
A. Ya. Malkin 107
The situation becomes even more complex if one considers properties of
monocrystals or reinforced plastics. Modulus of elasticity (and in fact all other
physical properties) of monocrystals depend on orientation of an applied force in
respect to crystallographic axes andit is quite possible to findsome different val
ues of modulus which depend on a type of crystal symmetry. In real
polycrystalline material, this effect is averaged, but it is not for monocrystals.
In reinforced plastics, modulus and all other mechanical properties depend on
orientation of a force in relation to orientation of reinforcing fibers and their ar
rangement. All this means that attempts to build the rheological equation of
state of such anisotropic materials, based on results of onedimensional experi
mental data, are absolutely futile. Instead, it is necessary to carry out a set of dif
ferent experiments for various geometries of deformation.
Anisotropic properties of material can be considered, within the limit of small
deformations, and in such a case, interpretation is a part of classical linear the
ory of elasticity. But modulus of elasticity of anisotropic materials must be
treated as a tensor by itself. Anisotropy of material properties is a particular
kind of rheological behavior of a material and it certainly does not exclude any
particular direction of all other rheological effects (for example, viscoelastic be
havior or thixotropy).
General principles of constructing rheological equations of state were intro
duced in modern rheological literature in some fundamental works, primarily
by Oldroyd,
49
Truesdell,
50
and Coleman et al.
51
The principles must be followed to
assure that at least some of the equations used for describing rheological effects
in deformation of real materials have physical meaning and the aboveformu
lated questions receive proper answers.
First of all, it is necessary to limit the use of tensor components for formulating
rheological equations of state because physical laws must not depend on choice
of coordinate system. This idea, which can be called the principle of coordi
nate invariance, requires all rheological relationships to be formulated
through invariants of an appropriate tensor but not through their components.
If the equation is written in invariants, it is still possible to discuss observed or
predicted effects in a convenient coordinate systemusing tensor components as
compounded variables.
In order to pursue this principle, it is convenient to introduce two fundamental
physical concepts related to deformations. They should describe the most gen
eral result of action of force. The first result of deformation can be accumulation
108 Rheological equations of state
of work of external forces in the form of elastic energy. This stored energy is
characterized by the value of elastic potential, W, whichis a specific stored en
ergy (energy related to the unit volume). The second possible result of deforma
tion is dissipation of work of external forces, i.e., its irreversible transition to
heat. This effect is characterized by intensity of heat dissipation, A, which is
a quantity of heat produced in a unitary volume of a material.
Introductionof the concept of elastic potential and intensity of heat dissipation
gives grounds for a very general classification of different materials:
• If during deformation, W≠ 0 and A= 0, a material has pure elastic response,
and it can be called an elastic body.
• If during deformation, A≠0 andW=0, amaterial is a pure viscous liquid.
• Finally, if during deformation only part of the work produced by external
forces is stored in a material and the other part dissipates, i.e., W ≠ 0 and
A ≠ 0, a material is a viscoelastic body.
These three types of rheological behavior will be discussed in the three subse
quent Chapters of the book.
The concepts of elastic potential and heat dissipation are very fruitful for for
mulating rheological equations of state, because bothvalues are physical objects
not connected to any coordinate system. When these concepts are used in rheo
logical equations of state, they must be represented as functions of invariants to
followthe principle of coordinate invariance. This canbe invariants of kinematic
(deformationor rate of deformation) or dynamic (stress) tensors but not their ar
bitrary components. Certainly, if the equation of state is formulated as a de
pendencies of W and A on invariants of kinematic or/and dynamic tensors, it is
always possible to arrive at the relationship between their components.
The direct consequence of the principle of coordinate invariance is the neces
sity to express scalar values, met in rheological equations of state, as functional
invariants of kinematic and/or dynamic tensors, but not of their components.
These scalar values are physical properties of an individual material. For exam
ple, it can be viscosity or modulus of elasticity. They can change under deforma
tion, but dependencies of the constants characterizing conditions of deformation
must enter into rheological equations of state only inthe formof functions of ten
sor invariants.
In the next step, physical laws should be related to the definite site (point) of a
material in a form that allows one to follow material moving in space. It means
that a rheological equationof state must describe behavior of a material, regard
A. Ya. Malkin 109
less of the possible motions of an observer. This approach has already been men
tioned in Chapter 3 in our discussion of large deformations and is called the
principle of material objectivity. The direct consequence of this principle is
the requirement of transformations of deformation and stress tensor frommov
ing to a fixed coordinate system (according to the rules of tensor transforma
tions) in order to give an observer the possibility to see what happens with a
material.
There are some other ideas which are also accepted in constructing rheological
equations of state. There is an easily grasped idea, stating that material has
memory of its prehistory (i.e., the manner of stress and deformationchanges can
influence the current state of material) but material cannot predict future
events. This is called a principle of determinism.
Also, it is considered as a general rule that only shortrange interactions are
important, i.e., stress and deformation behavior at some point are influenced
only by the nearest neighbors of this point, which is called a principle of local
action.
Although the abovecited principles are a general basis for formulating rheo
logical equations of state (constitutive equations) of various materials and are
considered as objective laws, it is possible to find real physical examples which
do not obey some of them. For example, for liquid crystals and other materials
possessing inner macrostructure, whichcannot be neglected, the idea of local ac
tion can be invalid.
Rheological equations of state must describe mechanical behavior of all possi
ble real materials. It is therefore important to answer the following question:
where is the place of individual properties of a material? There are two levels in
answering this question. First, the difference between behavior of various me
dia is reflected in the form of a rheological equation of state used to describe pe
culiarities of their deformational properties. Second, the difference of two
materials with similar rheological properties (i.e., expressed by the equivalent
rheological equations of state) is reflected in absolute values of scalar coefficient
entering the equation.
For example, water and steel are different materials, one of them is a liquid
and the second is a solid, and the difference in their properties is reflected by the
necessity to use quite different rheological equations of state for description of
their mechanical behavior, i.e., the Newton or Hooke Laws. Water and paint are
bothliquids but withdifferent specific behavior at various levels of stress; that is
110 Rheological equations of state
why we need to use different rheological equations of state for these two forms of
matter, though both of them are liquids. Finally, water and oil are both Newto
nian liquids and the distinction of their behavior is hidden in the difference of
their coefficient of viscosity.
4.3 CONCLUDING REMARKS
Investigating deformational properties of real materials, one encounters many
“new” effects compared with “ideal” models of a linear liquid (Newtonian liquid)
or a linear solid (Hookean solid). These effects must be treated as special rheo
logical phenomena. Understanding their origin, correlation with inherent
structure of matter, and quantitative description are the main problems dis
cussed in theoretical, experimental, and applied rheology.
The most important and evident rheological effects are:
• nonNewtonianviscosity dependence of apparent viscosity calculatedas
for Newtonian liquids for a particular geometry and flow conditions for dif
ferent rates of flow
• plastic behavior  lackof deformationif stress does not exceedsome critical
level
• Weissenberg effect  existence of normal stresses in shear flow, or appear
ance of a threedimensional stress state in unidimensional deformation
• transient (or timedependent) behavior. It can have numerous and inter
penetrating manifestations: thixotropy and rheopexy, i.e., reversible
change of inherent structure of matter, its destruction or building, under ap
plied stresses; dilatancy, i.e., reversible volume changes under shearing;
viscoelastic behavior, i.e., delayed deformation after stress application
(creep) or remaining stress after applying deformation (relaxation)
• anomalies in uniaxial extension  probability of uniform stretching at
large extension ratio, increase of longitudinal (extensional) viscosity as a
function of deformation and rate of extension
• flow instability, particularly melt fracture, which is not related to the
classical Reynolds inertial turbulence but connected withelasticity of a flow
ing liquid; appearance of secondary flows, and so on
• nonlinear elasticity as a result of large elastic deformations  compli
cated stress versus deformation dependence and consequences of geometri
cal nonlinearity, particularly the Poynting effect  extension of twisted
wires.
A. Ya. Malkin 111
Generally speaking, all rheological phenomena can be treated as nonlinear
effects, bearing in mind that they manifest themselves as a departure of me
chanical behavior of real material from the prediction of linear models, repre
sented by the Newton and Hooke Laws.
It is reasonable to distinguishbetweendifferent “degrees” of nonlinear behav
ior. Different rheological effects whichare nonlinear phenomena originate from
three general principle causes:
52
• Nonlinear effects can be caused by geometrical reasons and can be nothing
more than a direct consequence of large elastic deformation. Typical results
of such effects were discussed in Chapter 3, concluding that it is necessary to
introduce other measures of deformation to characterize the deformed state
of material. Such an approach allows one to exclude nonlinearity. It is rea
sonable to think that the Weissenberg effect (at least within the limit of very
lowrates of deformation) and the Poynting effect are two mainconsequences
of geometrical nonlinearity, or large elastic deformation. Nonlinear ef
fects of such kind are observed in static (or equilibrium) conditions or in slow
flows.
• Nonlinear effects can be related to changes (or “rupture”) of the inherent
structure of material. At different stresses available at various rates of de
formation, incomparable materials are encountered, having new values of
essential parameters, such as viscosity or elastic modulus. This type of
nonlinearity is the most typical for colloidal systems and filled polymeric
materials. Structural nonlinearity can be one of the reasons for
nonNewtonian viscous flow, and it is the cause of the Mullins effect. It is
worth noting that in discussion of structural nonlinearity, it is useful to add
kinetic arguments to rheological considerations.
• Strong nonlinear effect can be observed if material transits into a new
relaxational or phase state due to the action of deformation. Rheological
properties of material in different phase or relaxational state are quite dif
ferent because of changes along the transition. This type of rheological be
havior, which can be called phase nonlinearity, is encountered, for
example, during polymer crystallization in extension. Amorphous phase
separation is observed in flowing polymer solution or rupture of viscoelastic
stream(“melt fracture”) which occur at high rates of deformation. It is worth
mentioning that in discussion of phase nonlinearity, it is useful to add ther
modynamic arguments to rheological considerations.
112 Rheological equations of state
Based on the above discussion, it is possible to build a hierarchy of nonlinear
rheological effects, characterized by the following terms:
geometrical structural phase
weak strong breaking
static kinetic thermodynamic
Many real materials are multicomponent compositions. Different compo
nents of material can behave differently at the same rates of deformation, i.e.,
abovementioned types of nonlinearity can appear at different conditions of de
formation. For example, any real polymer is polydisperse, i.e., it consists of com
ponents of different rheological properties. Thus, a certain level of deformation
rate is sufficient for appearance of nonlinear behavior for a part of a material,
but this level of deformation rate might not be adequate to cause nonlinear be
havior of other components of the same system. It is also possible that different
modes of nonlinearity are characteristic for various components of complex ma
terial. For example, filled polymer melt can manifest nonlinear behavior of one
type, due to particular properties of a viscoelastic polymeric matrix, and the
other type due to rupture of the structure of a filler. It means that in real practi
cal application, superposition of various nonlinear effects of different types can
be expected.
As a general rule, rheological phenomena are observed in analysis of onedi
mensional deformation, although one of the most interesting characteristic rhe
ological effects is a limited probability of maintaining onedimensional stress
state for some materials.
Experimental points obtained under different conditions of measurement
(stress versus deformationor/and versus time) canbe approximated by different
equations. Thus, the central problem in rheology is the compatibility of equa
tions used for quantitative description of various rheological phenomena.
There are two sides to the problem:
• it is important to relate the explanations to analogous phenomena, but ob
served for different geometrical modes of deformation (for example, flow in
shear and extensionmust correlate  but how?), they need to be treated as re
lated consequences of the single relationship between forces and deforma
tions
A. Ya. Malkin 113
• it is of importance to correlate different rheological effects; for example,
nonNewtonian flow, normal stresses in shear, and large elastic deforma
tions in the quest to understand their common source.
In this aspect, the concepts of rheological equation of state occupy the cen
tral position in the description and generalization of experimental data. There
are some important (physical) limitations, determining the fact that not every
analytical equation can be used as a rheological equation of state. These limita
tions are expressed as the following principles:
• coordinate invariance  behavior of a medium does not depend on choice
of a coordinate system; that is why the rheological equation of state must be
formulated, not inthe formof components of stress and deformationtensors,
but as their invariants
• material objectivity  behavior of a mediumdoes not depend on movement
of an observer or a body as a whole
• determinism  a material can remember its past, which influences its be
havior in a current moment, but does not know future events
• local action  only the nearest surrounding may influence behavior of a
body at a point not the events happening far from this point.
In spite of all these limitations, freedom in constructing rheological equations
of state is rather wide. Therefore, it is very important to choose equations which
are not too complicated to be used for practical calculations and which can be
correlated with the physical structure (or content) of matter. The first is neces
sary for industrial and technological application of rheology, and the second is of
basic value if one considers rheology as one of the fields of physical chemistry of
fering background for objective quantitative characterization of the properties
of matter.
There are two possible general types of body reaction on the action of external
forces:
• storing the work in the form of elastic potential
• irreversible loss of this work by heat dissipation.
Inaccordance withthese fates of energy whichwas delivered by the work of ex
ternal forces, we can distinguish between elastic (solid) bodies and viscous liq
uids. The intermediate situation when the work done is partly stored and partly
dissipated is also possible, and this is the case of viscoelastic materials.
In construction of rheological equations of state, the elastic potential and in
tensity of heat dissipation must be expressed as functions of invariants of kine
114 Rheological equations of state
matic and/or dynamic tensors. The difference in mechanical behavior of various
materials is reflected in the form of the rheological equation used, and the val
ues of scalar coefficients (“material constants”) which are parameters of this
equation, customizing properties of a material.
The last general remark is rather evident for a rheologist but may look strange
for a nonprofessional or even for an engineer. From practical or technological
point of view, in the great majority of cases, one can definitely distinguish be
tween solid bodies and fluids, i.e., they are qualitatively different entities. For
rheology, the difference between them is quantitative rather than qualitative,
and it is preferable to qualify them, not into solids and liquids but as materials
with dominating solidlike and liquidlike behavior under real conditions. The
difference appears as a consequence of the ratio of the time scale (duration) of
observation and the inherent (characteristic) time scale of a material.
4.4 REFERENCES
1. W. Ostwald, Kolloid Z., 36, 99 (1925).
2. M. M. Cross in Polymer Systems. Deformation and Flow. Eds. Wetton and
Whorlow, Macmillan, 1968.
3. P. J. Carreau, Ph. D. Thesis, University of Wisconsin, 1969.
4. K. Y. Yasuda, R. C. Armstrong, and R. E. Cohen, Rheol. Acta, 20, 1263 (1981).
5. G. V. Vinogradov and A. Ya. Malkin, J. Polym. Sci., 2B, 671 (1964).
6. A. De. Waele, J. Oil. Colour Chem. Assoc., 6, 33 (1923). W. Ostwald, Kolloid Z., 36,
248 (1925).
7. E. C. Bingham, J. Physique, 9, 34 (1980); E. C. Bingham and H. Green, Proc. Amer.
Assoc. Testing Mater., II, 19, 640 (1919).
8. N. Casson in Rheology of Disperse Systems. Ed. C. C. Mill. Pergamon Press,
Oxford, 1959.
9. A. Nadai in Plasticity, McGraw Hill, New York, 1931; R. Hill in Plasticity. Claderon
Press, Oxford, 1950; W. Prager and P. G. Hodge in Theory of Perfectly Plastic
Solids. Wiley, New York, 1951.
10. K. Weissenberg, Nature, 159, 310 (1947).
11. G. V. Vinogradov, A. Ya. Malkin, E. P. Plotnikova, and V. A. Kargin, Doklady Akad.
Nauk USSR, 154, 1421 (1964).
12. A. Ya. Malkin, Rheol. Acta, 7, 335 (1968).
13. F. Trouton, Proc. Phys. Soc. Ind., 19, 47 (1905); Proc. Royal Soc. Ind. Ser. A, 77, 326
(1906).
14. J. Meissner, Rheol. Acta, 10, 230 (1971); Chem. Eng. Commun., 33, 159 (1985).
H.M. Laun and H. Münstedt, Rheol. Acta, 15, 517 (1976), ibid, 17, 415 (1978);
J. J. Linster and J. Meissner, Makromol. Chem., 190, 599 (1989).
15. R. G. Larson, Rheol. Acta, 31, 213 (1992).
A. Ya. Malkin 115
16. J. P. Tordella in Rheology. Theory and Applications, Ed. F. R. Eirich, vol. 5,
Academic Press, New York, 1969.
17. G. V. Vinogradov and A. Ya. Malkin, J. Polym. Sci., A2, 10, 1061 (1972);
G. V. Vinogradov, Pure Appl. Chem., Macromol Chem., 8, 413 91973); ibid
9, 115 (1973); Rheol. Acta, 12, 357 (1973).
18. A. Ya. Malkin and A. I. Leonov in Advances in Polymer Rheology, Khimia,
Moscow, 1970.
19. G. I. Taylor, Phil. Trans. Royal Soc., Ser. A, 223, 289 (1923).
20. H. Giesekus in Progress in Heat and Mass Transfer, Ed. W. R. Schowalter,
A. V. Luikov, and W. J. Mikowycz, Minsk, 5, 195 (1972).
21. G. Ver Strate and W. Philippoff, J. Polym. Sci., Polym. Letters, 12, 267 (1974).
22. R. E. Christensen, Soc. Plast. Eng. J. , 18, 751 (1962); C. J. S. Petrie and M. M. Denn,
AIChE J., 22, 209 (1976).
23. Lord Rayleigh, Proc. London Math. Soc., 10, 4 (1879).
24. M. Goldin, H. Yerushalmi, R. Pfeffer, and R. Shinner, J. Fluid Mech., 38, 689 (1969).
25. J. S. Lazurkin, J. Polym. Sci., 30, 595 (1958); S. S. Sternstein, L. Ongchin,
and A. Silverman, J. Appl. Polym. Symp., 7, 175 (1968).
26. T. B. Benjamin, J. Fluid Mech., 2, 554 (1957).
27. B. A. Toms, First Intern. Congr. Rheol., vol. II, p. 135, North Holland Publ.,
Amsterdam, 1949.
28. J. L. M. Poisseuille, Compt. rend., 11, 961 1041 (1840); ibid, 12, 112 (1841); ibid, 15,
1167 (1842).
29. H. Blasius, Z. de Ver. deutscher Ing., 639 (1912).
30. P. S. Virk, J. Fluid Mech., 45, 225 (1971); AIChE J., 21, 625 (1975).
31. H. Freundlich in Thixotropy, Hermann and Co., Paris, 1935.
32. O. Reynolds, Phys. Mag., 20, 469 (1885); Nature, 30, 429 (1886).
33. W. H. Bauer and E. A. Collins in Rheology. Theory and Applications,
Ed. F. R. Eirich, vol. 4, p. 423, Academic Press, New York, 1967.
34. A. V. Tobolsky, J. Appl. Phys., 15, 309 (1944).
35. A. Ya. Malkin and S. G. Kulichikhin in Rheokinetics, Hüttig and Wept, Heidelberg,
1994.
36. E. Guth and H. Mark, Monatsch, 65, 93 (1934); W. Kuhn, Kolloid Z., 68, 2 (1934).
37. E. Guth, H. M. James, and H. Mark, Adv. Colloid Sci., 2, 253 (1946).
38. G. M. Bartenev and T. N. Kazanovitch, Vysokomol. Soed., 2, 20 (1960).
39. M. J. Mooney, J. Appl. Phys., 11, 582 (1940); R. S. Rivlin and D. W. Saunders, Phys.
Trans. Roy. Soc., A243, 251 (1951).
40. P. J. Blatz, S. C. Shrada, and N. Tschoegl, Trans. Soc. Rheol., 18, 145 (1974).
41. R. W. Ogden, Proc. Roy. Soc., 326, 565 (1972).
42. J. H. Poynting, Proc. Roy. Soc., Ser. A, 82, 546 (1909); 86, 534 (1912).
43. J. Barus, J. Am. Chem. Soc., 45, 87 (1893).
44. J. L. White, Trans. Soc. Rheol., 19, 271 (1975).
45. L. Mullins, J. Rubb. Res., 16, 275 (1947).
46. Lord Kelvin (W. Thomson) in Elasticity. Encyclopedia Britannica, 9th Ed., 1875.
116 Rheological equations of state
47. W. Voigt, Abh. Ges. Wiss. Göttingen, 36, (1890); Ann. Phys., 47, 671 (1892).
48. J. C. Maxwell, Phys. Mag., 35, 129, 185 (1868).
49. J. G. Oldroyd, Proc. Roy. Soc., Ser. A, 200, 523 (1950); ibid, 202, 345 (1950.
50. C. Truesdell in Principles of Continuum Mechanics. SaconyMobil Oil Co., Texas,
1961.
51. B. D. Coleman, H. Markovitz, and W. Noll in The Viscometric Flows of
NonNewtonian Fluids, Springer, Berlin, 1966.
52. A. Ya. Malkin, 4th Eur. Rheol. Congr., Seville, 1994; Rheol. Acta, 34 (1995) in press.
A. Ya. Malkin 117
5
RHEOLOGICAL VISCOUS FLUIDS
5.1 DEFINITIONS
The concept of a liquid seems rather evident. Nobody doubts that water or
gasoline are liquids. But what about tooth paste or adhesive? These simple ex
amples showthat it is not sufficient to imply that a liquidis a material whichcan
flow. It is necessary to introduce a more rigorous definition and compare behav
ior of real materials with such a definition.
We may think that a liquid is a material which undergoes unrecoverable (ir
reversible) deformations, i.e., changes in shape remain after the action of ex
ternal forces is removed. It should be noted that the definition must encompass
all real materials. For example, one would need to consider metals as liquids be
cause during some technological operations, e.g., punching of golden articles,
wiredrawing of silver or rolling steel ingots, we undoubtedly create unrecover
able deformations. These examples show that the above definition is too wide.
Indeed, it covers two types of behavior: viscous and viscoplastic. In the first
case, unrecoverable deformations (or flow) can be detected at any stress, re
gardless how small it may be. In the second case, unrecoverable deformations
appear only when stress overcomes some definite level, which is called yield
stress or yield point. It means that a viscoplastic mediumcan be called a “liq
uid” only with some precautions. Nevertheless, treating deformation of
viscoplastic materials, at stress exceeding yield stress as a flow, looks quite rea
sonable.
A. Ya. Malkin 119
We can also define a liquid as a material which can flow (or is capable of unre
coverable deformations) under the action of infinitesimal (small) stress.
Formally, this definitionlooks quite acceptable. But anexperimentator may ask
two questions:
First: Perhaps if stress is decreased by one (two, three, etc.) orders of magni
tude, it is possible to reach the yield point at which flow, at very lowstress, does
not occur, i.e., in the case of any liquid, one deals with a viscoplastic liquid, but
the yield stress is so small that it cannot be observed under experimental condi
tions but canbe attained if conditions change. This assumptionmay have rather
serious consequences. Doubt was expressed even for such a classical liquid as
water. Indeed, it is never certain that the level of stress attained in an experi
ment is sufficiently low to assume that a material is a liquid from an experi
mental point of view.
The possibility to flow under infinitesimal stress means that a liquid at rest
cannot store any stress. Indeed, if outer boundaries of body (treated as a liquid)
are motionless, no stress should exist in the whole volume of the body. This is
true with some reservations only. For example, flow inside a body having mo
tionless boundaries can appear as a result of temperature gradient in a liquid.
Nevertheless, this idea can also be considered as a definition of a liquid state.
Contrary to such behavior, liquid viscoplastic media (“liquids”) can store resid
ual stresses equal to the yield stress.
Second: Perhaps during the period of observation (or experiment) unrecover
able deformations are so small that they cannot be detected, even though they
exist. If an experiment is prolonged, flow of a material under investigation
should occur.
Rheologists like to cite a famous exclamation by the Bible’s Deborah: “The
mountains meltedfrombefore the Lord”, bearing inmindthat inthe scale of eter
nity, the Lord really can observe flowof rocks (mountains). That is true, and the
general answer to the problem raised by the theoretician lies in the comparison
of “inherent” time scale of a material, t
inh
, and time of observation, t
obs
. This char
acteristic inherent time, t
inh
, canbe treated as time of relaxation, i.e., time neces
sary for recovery of a stable structure state after removal of external forces.
Then, we can introduce the dimensionless criterion t
obs
/t
inh
(see also Eq 4.17),
called the Deborah Number, De:
De = t
obs
/t
inh
120 Rheological viscous fluids
If De > 1, material behaves like a liquid, which occurs when t
inh
is small and re
laxation happens very quickly (in comparison with time of observation). In the
opposite time scale (when De < 1), unrecoverable deformations cannot be de
tected and we cannot discover flow and treat a material as a liquid.
We then can define liquid as a material which relaxes very quickly, and this
definition gives the concept of liquid, not as a state of a matter, but as a kind of
behavior. Therefore, one should consider liquidlike behavior of a material,
which answers the second question regarding rigorous definition of a liquid.
Finally, a very general definition of a liquid might be constructed on the basis
of energy concept (see Section 4.2). Any action is connected with energy con
sumption. Two types of energy used for material deformation might be consid
ered: the energy stored in the material and its return after the removal of
external forces. Storage of energy is characteristic for an elastic medium(elastic
behavior in rheological media is discussed in Chapter 6). The second reaction
consists of energy dissipation by its conversion to heat, which is characteristic
for viscous liquids, because viscous resistance to movement means heat dissipa
tion of the work produced by the forces applied.
A viscous liquid then, can be defined as a medium deformed in such a manner
that energy needed for deforming completely dissipates in the process of
deformation. In essence, it means that no energy source for further deformation
exists in the material after the action of external forces ceases and that is why
deformation cannot be recovered (no driving force exists for the process).
Certainly, intermediate cases may exist when energy of deformation is partly
stored in a material and only part of this energy can be dissipated. Such is the
case of a viscoelastic body, inparticular, of a viscoelastic liquid. We shall not con
sider such liquids here, only a viscous liquids, without any elastic effects, since
all of Chapter 7 is specifically devoted to media properties having a combination
of viscosity and elasticity.
The energy concept dividing materials according to their reaction to the work
of deformation is the most general approach of characterization of a material
type. Such a concept is not related to any considerations of local values of
stresses and deformations and does not need to be related to observation of ma
terial behavior in coordinate axis. In this sense, the energy approach is invari
ant to a coordinate transformations and satisfies general requirements of
rheological equations of state.
A. Ya. Malkin 121
5.2 NEWTONIAN LIQUID
The idea of Newtonian and nonNewtonian behavior of liquids was intro
duced in discussion of rheological effects describing the development of rheology
as a separate branch of natural science (Chapter 4). We shall nowdiscuss a gen
eral approach to the concept of Newtonian liquid, bearing in mind the common
principles of rheology formulated in Chapter 4.
Onedimensional (trivial) definition of Newtonian (or NewtonStokes) liquid is
given in Eq 1.1 for simple shear. It is very easy to convert this equation, using
tensor notation:
σ η
ij ij
= 2 D [5.1]
and for simple shear
& γ = 2D =
u
x
ij
1
2
∂
∂
[5.2]
which refers to the standard definition, Eq 1.1. Further discussion concerns the
concept of a Newtonian liquid in an invariant form.
In order to apply the definition of a liquid as a material for which all work done
indeformationdissipates, one needs to express the intensity of dissipation, A, as
a function of deformation rate in a rheological definition of a liquid. The A is a
physical object invariant to the choice of a coordinate system, which is why the
rate of deformation also must be represented through its invariants.
This general approach allows for the following definition of the Newtonian liq
uid:
A = 4 D
2
− η [5.3]
where D
2
is the second invariant of the rate of deformation tensor.
Intensity of dissipation, A, is expressed as
A =
ij ij ∑
σ γ&
where σ
ij
are components of the stress tensor, & γ
ij
are components of the rate of
deformation tensor, and ηis (Newtonian) viscosity.
122 Rheological viscous fluids
The second invariant of the rate of deformation tensor is
D = + + ( + + )
2 11 22 11 33 22 33 12
2
13
2
23
2
& & & & & & & & & γ γ γ γ γ γ γ γ γ −
Combining the expressions for Aand D
2
withthe definition, Eq 5.3, and consid
ering coefficients in tensor notations, one comes to the starting formula of the
NewtonStokes liquid, Eq 1.1.
It is interesting and instructive to draw the relationship between stress and
rate of deformationfor uniaxial elongationbased onthe general (invariant) defi
nition, Eq 5.3.
Stress tensor for uniaxial extension is expressed as
σ σ
11 E
=
whereσ
E
is the drawing stress and all other components of the stress tensor are
absent (equal to zero).
The rate of deformation tensor has only diagonal nonvanishing terms. It
should be assumed that a liquid is incompressible. In this case (see Chapter 2),
the first invariant of the deformation tensor equals zero. Thus, its time deriva
tive (i.e., the first invariant of the rate of deformation tensor) also equals zero
and we have
D = + + = 0
1 11 22 33
& & & γ γ γ [5.4]
For an axially symmetrical body, for example, for a cylinder,
& & & γ γ γ
22 33 11
= =
1
2
−
Therefore, A is evidently equal to
A =
11 11
σ γ&
For uniaxial extension, considering relationship between components of the
rate of deformation tensor, we have
A. Ya. Malkin 123
D =
3
4
2 11
− & γ
which leads to the following relationship between drawing stress and rate of de
formation in uniaxial extension
σ ηγ
E 11
= 3 & [5.5]
The coefficient between normal stress, σ
E
, and the rate of deformation is called
elongational viscosity, λ, and according to Eq 5.5
λ η ·3
which is Trouton equation, discussed above. In fact, it demonstrates that both
equations (Newton and Trouton equations) represent the same type of rheologi
cal behavior, i.e., the Newtonian liquid (liquid obeying the Newton Law in
shear) will obey the Trouton Law in uniaxial extension and vice versa.
The same result canbe obtained, not only by using the idea of intensity of dissi
pation, but also by exploring the decompositionof stress andthe rate of deforma
tion tensors into spherical and deviatoric parts.
The stress tensor can be decomposed into spherical and deviatoric parts in the
following manner:
σ
σ
σ
δ
σ
=
0 0
0 0 0
0 0 0
=
3
+
3
2 0 0
0 1 0
0 0 1
E
E
ij
E
















where the first member is a spherical part (negative hydrostatic pressure) and
the second term is a deviator of the stress tensor.
For uniaxial stretching of a symmetric body, using the above mentioned rela
tionship between components of the rate of deformation tensor, we can write:
124 Rheological viscous fluids
&
&
&
&
& γ
γ
γ
γ
γ =
0 0
0 0
0 0
=
1
2
2 0 0
0 1 0
0 0 1
11
22
33
11
















The spherical component in the rate of deformation tensor is absent which is the
consequence of the incompressibility of liquid. The spherical part in the stress
tensor is present but its value is immaterial for rheological behavior of liquid(re
gardless of the hydrostatic pressure, the volume of liquid remains unchanged).
If we compare deviatoric parts of both tensors, we again come to the Trouton
equation for elongational viscosity, which equals 3η.
The general definition(Eq 5.3) of the Newtonianliquid also allows one to calcu
late elongational “viscosity”, now measured in biaxial extension.
Let us find the relationship between drawing (normal) stresses, σ σ σ
E 11 22
= = ,
(σ
33
equals zero) and rate of deformation, & & & ε ε ε = =
11 22
. According to Eq 5.4, in
this case, & ε
33
0 · .
For biaxial extension
A = 2 ; D = 3
E 2
2
σ ε ε & & −
and then in accordance with fundamental Eq 5.3, we have
σ ηε
E
= 6 & [5.6]
It is possible to treat the coefficient of this Equation (i.e., the coefficient of pro
portionality betweenstress andrate of deformation) as elongational viscosity, in
the same manner as done for the Newton and Trouton Laws. Then, the biaxial
“elongational viscosity” equals6η(not 3ηas in uniaxial extension). These two
examples (uniaxial and biaxial extension) showthat “viscosity” of a liquid canbe
different, depending on its definition.
These simple examples demonstrate that results of different experiments can
be considered as consequences of the same rheological equation of state (consti
tutive equation) if formulated ina generalized (tensor) form. Also, it is clear that
invariants must be used in the formulation of rheological equations of state for
liquids in relationships between components of stress and rate of deformation
tensors.
A. Ya. Malkin 125
ANewtonian liquid is the simplest incompressible linear liquid and its rheo
logical properties are completely described by a single parameter, its shear vis
cosity. In fact, it implies that a liquid is isotropic. But anisotropic liquids, i.e.,
liquids with properties dissimilar in different directions, can also exist (for ex
ample, in liquid crystals). Even if such liquid is linear, a single coefficient of vis
cosity is not sufficient for complete representation of its viscous properties. If we
measure viscosity by creating shear at different planes, we will obtain dissimi
lar values of “viscosity”.
1
For such anisotropic liquids, it appears necessary to
characterize their properties by a tensor of viscosities,
1
though practical de
termination of components of this tensor can appear a very complex problem.
In order to give an impression of the possible range of changes of viscosity for
real liquids let us list some typical values:
Gases 0.1 mPa⋅s
Water (at 20
o
C) 1 mPa⋅s
Sulphuric acid 30 mPa⋅s
Lubricating oils 0.1  3 Pa⋅s
Glycerin 2 Pa⋅s
Oligomers 10 mPas  10 Pa⋅s
Glues, paints 1  200 Pa⋅s
Melts of thermoplasts 100 Pas  100 kPa⋅s
Rubbers and rubber compounds 10 kPas  10 MPa⋅s
Bitumens 100 kPas  100 MPa⋅s
Melted inorganic glasses 1 MPas  100 GPa⋅s
Glassy liquids 100 GPa⋅s
The viscosity of liquids can vary in a wide range of values exceeding 15 decimal
orders.
5.3 NONNEWTONIAN LIQUIDS
According to the discussion in Chapter 4, any viscous liquid is a medium for
which intensity of heat dissipation in deformation is expressed as a function of
kinematic and/or dynamic invariants. The simplest equation representing the
idea is the Newton Law written as Eq 5.3. Certainly this equation does not de
scribe other effects characteristic for nonNewtonian liquids.
126 Rheological viscous fluids
The formal way of generalization was proposed by Rivlin
2,3
who advanced the
idea that intensity of energy dissipation is a linear function of the second and
third invariant of the deformation rate tensor. This assumption can be written
as
A = 4 D + D
2 c 3
− η η [5.7]
where the first member is Newtonianinput to stress tensor andthe secondone is
a nonNewtonian addition. The coefficient of proportionality, η
c
, is called
“crossviscosity”.
The dissipative function (Eq 5.5), describing behavior of the Reiner liquid,
predicts the existence of normal stresses (Weissenberg effect) as a secondorder
phenomenon(normal stresses are proportional to the squared shear rate) but no
other special rheological effects, including nonNewtonian viscosity. Moreover,
the predicted sign of a normal stress is opposite to experimentally observed val
ues. It is important to emphasize that in the Reiner liquid, normal stress ap
pears for pure viscous medium(stored elastic energy is absent) but is not related
to rubbery elasticity of a material. It also contradicts the experimental evidence,
because we know that normal stresses always accompany, or are accompanied
by large elastic deformations.
The model of the linear Reiner liquid does not reflect the mechanical behavior
of any real material known to date; nevertheless, this model is very interesting
for two reasons: firstly, it shows the rigorous way of generalizing a rheological
equation of state through introducing different invariants of the kinematic ten
sor; secondly, it shows that not every formal way of constructing rheological
equations of state leads to realistic results. Bearing this conclusion in mind, the
Reiner viscous liquid model mostly has historical relevance.
Development of ideas concerning construction of rheological models of
nonNewtonian behavior takes various routes. First of all, the third invariant
was not used as an argument in rheological equations of state. Then the second
invariant of the rate of deformation tensor was used as an argument for a scalar
material constant, identifying properties of a material. It reflects the idea that
deformation influences the inherent properties of a medium, and this is the rea
son for nonNewtonian behavior.
A. Ya. Malkin 127
For onedimensional deformation, this concept can be written in the following
form
σ η γ
ij 2 ij
= 2 (D )& [5.8]
According to this equation, we assume that rate of deformation (expressed
through its second invariant) influences apparent viscosity of a liquid. The form
of the function η(D
2
) can vary, depending on individual properties of material.
Certainly, this equationcanbe treatedas a generalizationof Eq 5.3, andinthis
case, it is written as
A = 4 (D )D
2 2
− η [5.9]
One of the most popular (widely used for various applied calculations) models
of nonNewtonian flow is a power law, written as
σ γ = K
n
&
Apparent viscosity in this model is a decreasing function of shear rate or shear
stress
η
σ
γ
γ σ = = K = K
1
n
n1
n1
n
&
& [5.10]
and as a rule n < 1. A generalized (threedimensional) form of the power law
takes the following form
σ γ
ij
2
n1
n
ij
= 2K
1
2
D

.
`
,
& [5.11]
For onedimensional shear flow this equation can be written as
σ γ γ = K
n1
& &
where apparent viscosity is expressed as in Eq 7.10.
Eq 5.10 can be applied to unidimensional axial extension of a liquid cylindrical
128 Rheological viscous fluids
stream. In this case, components of the rate of deformation tensor are
&
&
& &
&
& γ λ γ γ λ γ
11 22 33 ij
= ; = =
1
2
; = 0 for i j − ≠
where the first component of the rate of deformation tensor is the rate of exten
sion. The D
2
can be found from equation
D =
3
4
2
2
−
&
λ
Let us suppose that, as usual, apparent viscosity is a decreasing function of
shear rate (and of D
2
). It means that ina threedimensional generalizationof the
power law, one may expect that the function η(D
2
), as the invariant characteris
tic of a material, must be decreasing as well. This leads to the conclusionthat the
increase of rate of extensional deformation must cause the decrease in apparent
viscosity, measured in uniaxial extension. Moreover, one can see that if we take
the condition between shear and extensional rate of deformation as
&
& λ γ =
1
3
we arrive at the Trouton Law, which becomes true for any viscous liquid at ap
propriate condition of comparison between shear and extension.
On the other hand, we know that for many “rheological” liquids the Trouton
Lawis not correct, whichis apparently not relatedto nonNewtonianbehavior of
a purely viscous liquid but is hiddeninits other rheological properties, infact, in
its elasticity. The divergence fromthe Trouton Lawin properties of some liquids
demonstrates that the possibility of describing properties of a liquid by equation
in one geometrical mode of deformation does not automatically lead to correct
ness of its threedimensional generalization and its application to another mode
of deformation. Indeed, viscous properties of two liquids can be the same in
shear but quite different in uniaxial extension.
A. Ya. Malkin 129
5.4 VISCOPLASTIC LIQUIDS
Rheological equation of state for a viscoplastic liquid was introduced in Chap
ter 4. Onedimensional rheological properties of a Binghamviscoplastic me
dium are expressed by Eq 4.7. The main problem in generalization of the
Bingham equation is the formulation of a threedimensional criterion of
yielding. This problem is typical in finding the threedimensional criterion of
strength in mechanics of rupture of solids or plasticity for solid plastic materi
als. The common question is: how to write the condition of rupture in a compli
cated (threedimensional) scheme of loading, if the strength of material was
measured in unidimensional extension.
Certainly, the answer to bothanalogous questions (regarding the strengthand
the yield stress) lies in the use of invariants of the stress tensor, and this crite
rion must be formulated through invariants of the stress tensor.
As a general rule, the influence of the hydrostatic pressure (or the first invari
ant of the stress tensor) is immaterial in a rheological problem, if pressure is not
very high. This fact has been already mentioned in discussion of the
Weissenberg effect in Chapter 4. The criterion of yielding for different main
stresses must be found, and the yield stress, σ
yE
, should be a function of the sec
ond invariant of the stress tensor. This approach is equivalent to the one used in
the theories of strength of solids. Moreover, the main analytical approximations
used in these theories also are used for the yield stress.
Different conditions (criteria) of the threshold of yielding (strength, plasticity)
in multidimensional loading were proposed and used. The most popular and
simple equationfor the yieldstress is basedonthe oldidea whichdetermines the
meaning of the critical value of the maximal shear stress (the Treska 
SaintVenant criterion). It assumes that if the yield stress in simple shear is
σ
yE
, the same material being stretched in one direction begins to flowat normal
stress, σ
E
, calculatedas (see relationships betweennormal andshear stresses in
Chapter 2):
σ σ σ σ
E yE yE E
= 2 ; = 0.5 [5.12]
Then, if the principle stresses in a multidimensional stress field are σ σ
1 2
, ,
and σ
3
, the Treska  SaintVenant criterion of yielding is given by
130 Rheological viscous fluids
 
2
;
 
2
;
 
2
1 2
yE
1 3
yE
2 3
yE
σ σ
σ
σ σ
σ
σ σ
σ
−
≤
−
≤
−
≤
An alternative approach used for determination of the threshold of yielding is
known as the von Mises criterion and is assumed as a condition of reaching
some critical value of the intensity of shear stresses. It is formulated through
principle stresses as
( ) + ( ) + ( ) = 2
1 2
2
1 3
2
2 3 yE
2
σ σ σ σ σ σ σ − − − [5.13]
where σ
E
is the yield stress in uniaxial extension.
It is interesting to note that the von Mises criterion of yielding can be called an
energetic criterion, because it is possible to showthat the left side of Eq 5.13 rep
resents (for the Hookean solid) specific energy of elastic deformation required to
change the formof a body (calculated for a point). It means that the material be
gins to flowwhenit has stored a critical amount of elastic energy while changing
its form (not volume, since we do not take into account the first invariant of the
stress tensor).
The correspondence between the shear yield stress and the critical normal
stress, according to the von Mises criterion, can be written as
σ
σ
σ
yE
E
E
=
3
0.577 ≈ [5.14]
Comparing Eqs 5.12 and 5.14, one can see that Treska  SaintVenant and von
Mises criteria are rather close to each other.
5.5 SOME BASIC PROBLEMS
5.5.1 INTRODUCTION
Some basic problems of hydrodynamics are discussed belowin order to demon
strate typical examples of application of rheological equations of state for main
types of “rheological” liquids. The term“hydrodynamic” should not lead to con
fusion. Use of this termdoes not imply that it is relatedspecifically to water (“hy
dro”) but to any viscous fluid.
A. Ya. Malkin 131
The transition fromrheological equation of state (or constitutive equation) of a
liquidto a hydrodynamic problemis equivalent to the transitionfromdiscussing
the situation “at a point” to considering flow of a liquid in a volume. It requires
one to combine the following elements:
• rheological equation of state (see Chapter 4)
• equilibrium(balance) equations (see Chapter 2); in the isothermal case, it is
an equation of force balance only
• boundary conditions.
The last element is yet to be defined. The use of boundary conditions is very
typical and common for solving any differential equation. Below, we shall dem
onstrate the importance of this factor for hydrodynamic problemsolving in a
volume.
In the subsequent sections, we shall discuss basic hydrodynamic patterns
which are most frequently observed in applications. Real situations can be very
complex; at the same time, they can be expressed by relatively simple models.
The choice of examples discussed belowis determined by the possibility to inte
grate differential equations of flow to obtain a solution in analytical form. It is
done only for illustrative purposes, because equations of flowfor practically any
geometrical pattern (even very complex) can be solved numerically, with desir
able accuracy, by computer calculations. This is also true for different rheologi
cal equations of state which are used for investigation of various hydrodynamic
situations. In this respect the majority of solutions discussed beloware exact so
lutions, contrary to their solutions obtained by computational methods, which
are approximate solutions, even though their divergence froman exact solution
can be as small as required.
All examples discussed in this Section are related to laminar flow and are not
applicable to turbulent flow. Meanwhile, turbulence can be considered as
nonNewtonian (“rheological”) flowof some special kind, because in a turbulent
regime the NewtonStokes relationship between shear stress and shear rate is
not valid, and as a consequence, for example, the relationship between flowrate
and pressure in flow through a channel appears to be different than predicted
for a Newtonian liquid.
The solutionof different hydrodynamic problems includes understanding of:
• distribution of hydrostatic pressure and components of the velocity vector in
space in which flowtakes place; four variables are functions of four basic hy
132 Rheological viscous fluids
vation of mass)
• integral characteristics of stream, suchas complete force appliedto a moving
body, output (or flow rate) of a liquid flowing through a channel, and pres
sure which must be applied to create predetermined flow rate.
Flowin different geometrical forms is used for numerous applications. Among
them are:
• problems of transportation of different liquids (socalled inner problems 
flow of liquids inside channels with solid external boundaries)
• movement of solid bodies inliquids (socalledouter problems  a liquid flow
around solid boundaries)
• purely rheological problems, such as comparison of theoretical predictions
with experimental observations (cannot be solved “at a point” but only for
volumetric flow) or determination of constants in rheological equations of
state.
First, two items on the list can be formulated for any space situation and arbi
trary geometry of solid boundaries of a channel or moving solid body, because
they are determined by the practical value of the situation under discussion.
The problems of the third group are considered, as a general rule, for rather sim
ple geometrical forms of solid boundaries, because only for such simple forms is
it possible to build an apparatus for comparison of theoretical prediction and ex
perimental observation resulting in an evident and easytograsp result.
5.5.2 PLANE UNIDIMENSIONAL FLOW
Figure 5.1 explains the exam
ple. Let us consider flow along
the zaxis, then assume that
the size of parallel planes in
xdirection is unlimited (at
least much larger than the dis
tance between planes equal to
H), which allows one to neglect
all changes which can happen
along the xcoordinate. It
means in particular that
A. Ya. Malkin 133
Figure 5.1. Scheme of plane unidimensional flow and
system of coordinates used for formulating basic hy
drodynamic equations.
drodynamic equations (three balance equations and an equation of conser
V = 0;
V
x
= 0;
p
x
= 0
x
∂
∂
∂
∂
Besides
∂
∂
∂
∂
V
z
= 0;
p
y
= 0
This shows that there is only one component of velocity, V
z
, different fromzero
(therefore, belowwe shall use the symbol Vwithout subscript index). Vcan be a
function of the ycoordinate only. Pressure can be a function of the zcoordinate
only, i.e.,
V = V(y); p = p(z)
Steady flow is considered, and therefore any inertial effect does not need to be
taken into account and inertial members in the equilibrium equations can be
omitted.
Consequently, there is a need for only one balance equation:
dp
dz
=
d
dy
−
σ
[5.15]
where
σ σ σ ≡
yz zy
=
The lefthand side of this equation is a function of z only, and the righthand
side member is a function of y only. It means that equality can exist if both mem
bers are constant. Then, the general solution of Eq 5.15, considering the bound
ary conditions, can be written as
σ σ =
dp
dz
y
w
− [5.16]
134 Rheological viscous fluids
where σ
w
is the shear stress acting (or applied) at the solid boundary (at the
plane). If the area of planes is S and total tangential force F, then
σ
w
=
F
S
It is important to emphasize that the general solution(Eq 5.16) is not relatedto
any rheological model, i.e., it is valid for any material. It is true because as long
as stress, but not velocity distribution, is discussed, it does not involve any rheo
logical equation of state.
The last general postulate should include the gradient of pressure. Assuming
that
dp
dz
= const
one can write
dp
dz
=
P
L
∆
where ∆P is the pressure drop (difference of pressures at the ends) in a channel
where flow takes place, and L is the length of this channel.
(i) Drag flow. The important case of Eq 5.16 includes flow in the absence of a
pressure gradient: dp/dz · 0, when
σ σ = = const
w
In this case, shear stress is uniform throughout the whole volume between
planes, regardless of rheological properties of a liquid. This type of flowis possi
ble when one plane is moved relative to the other and “drags” a liquid. This type
of behavior is called drag flow. Because shear stress is constant throughout a
gap between planes, the shear rate must be also constant (in steady flow), since,
for any nonNewtonian liquid, shear rate is an unambiguous function of shear
stress
A. Ya. Malkin 135
dV
dt
= const
which gives a linear velocity profile through a gap between planes:
V = V
y
H
w
where V
w
is the velocity of a moving plane (velocity of the other plane is assumed
to be equal zero).
The last equation can be rewritten in dimensionless form
V
V
=
z
β [5.17]
where β is a dimensionless coordinate
β=
y
H
The solution (Eq 5.17) is represented in Figure 5.2. The presence of linear ve
locity profile andconstant shear rate inthe gapis evident. Constant shear stress
leads to a constant rate of shear. The volumetric output, Q, in drag flowis calcu
lated as
Q=
V
2
BH
w
[5.18]
where B is the size of planes in the xdi
rection.
The possibility to realize flow with con
stant shear stress is an unique method of
constructing flow curves. Varying shear
stress (changing total force), the shear
rate is determined by the ratio
136 Rheological viscous fluids
Figure 5.2. Velocity profiles in flow
between two parallel planes without
pressure gradient.
& γ =
V
H
w
[5.19]
Then, the pairs of values “shear stress  shear rate” are obtained.
The experiment can be reversed: we can set velocity, V
w
, of a moving plane,
measure total force, F, and calculate shear stress as the ratio of F/S.
In practical realization, it is not necessary to have flat planes; they can be
curved into cylinders. Circular drag flow between two coaxial cylinders was in
vestigated by Couette,
1
and thus the problem is called the Couette problem.
Also, other drag flows (not only circular) are often called the Couette problem. If
the gap between two coaxial cylinders is much smaller than their radii, one can
neglect their curvature and treat them as parallel plates.
Let the radius of the outer cylinder be R
o
, the radius of the inner cylinder R
i
,
and the condition
R R
R
<<1
o i
o
−
[5.20]
is fulfilled. The systemof two coaxial cylinders is thentreatedas parallel planes
H= R R ; S= 2
R + R
2
L
o i
o i
− π
where L is the height of the cylinders.
Linear velocity is expressed as
V = R ω
whereωis angular velocity (measured in rad/s), Ris the radius of an outer or in
ner cylinder which are almost the same if the condition 5.20 is valid.
The shear rate in the gap is
& γ
ω
=
R
R R
o i
−
[5.21]
A. Ya. Malkin 137
The existence of shear stresses leads to torque, M, expressed as
M= 2 R H = 2 R H
o
2
o i
2
i
π σ π σ [5.22]
where His the height of cylinders (more exact: height of a gap filled with flowing
liquid).
The last equation allows one to estimate the inhomogeneity of stress field in
the gap between two coaxial cylinders. Since M = const,
σ
σ
α
i
o
o
i
2
=
R
R

.
`
,
≡
If R
o
/R
i
is close to 1, then we have an “almost” homogeneous stress field.
This configuration is often used in viscometric practice in socalled rotational
viscometers. The most important point here is the possibility to find shear stress
and shear rate independently and regardless of any rheological model, i.e., this
configuration can be treated as an absolute method of determining a flow curve
of a nonNewtonian liquid with unknown rheological properties. Certainly, this
method works when the condition 5.20 is fulfilled. If we know shear stress from
the torque (Eq 5.22) and shear rate from angular velocity (Eq 5.21), we can eas
ily find apparent viscosity in accordance with the NewtonStokes definition of
“viscosity”:
η
σ
γ π ω
≡
−
&
=
M(R R )
2 R H
o I
o
3
[5.23]
where it is assumed that an outer cylinder is rotating and M is the torque mea
sured also for an outer cylinder. Changes in Eq 5.23 must be introduced if an in
ner cylinder is rotating, or if we measure the torque appliedto aninner cylinder.
If the gap between cylinders is not small in relation to the radius of the inner
cylinder, the general solution for a liquid with arbitrary rheological properties
does not exist. Indeed, velocity distribution in circular flowbetween two coaxial
cylinders with an arbitrary (not an obligatory small) gap between themdepends
on rheological properties of a liquid. The exact solutions can be found for some
shear rate versus shear stress laws. The simplest case is surely a Newtonianliq
138 Rheological viscous fluids
uid. In this case, when an outer cylinder is rotating with angular velocity, ω
o
,
and angular velocity of an inner cylinder is ω
i
, velocity distribution is expressed
by a formula
V(r) =
( R R )r + ( )R R
(R r )r
o o
2
i i
2 2
o i i
2
o
2
o
2
i
2
ω ω ω ω − −
−
[5.24]
where Vis the V
ϕ
(circular) component of the velocity vector andr is a current ra
dius ( R
o
> r > R
i
). Special cases, whenω ω
o i
= 0or = 0, are formally included in Eq
5.24.
The distribution of shear stress is
σ
η ω ω
=
2 ( )R R
(R R )r
o i o
2
i
2
o
2
i
2 2
−
−
[5.25]
where ηis viscosity of a Newtonian liquid.
The torque in flow of a Newtonian liquid is expressed as
M=
4 L( )R R
R R
o i i
2
o
2
o
2
i
2
πη ω ω −
−
[5.26]
The torque is the same for any value of radius, which is why the current radius,
r, does not enter Eq 5.26.
Eq 5.26 is the basic equation for determination of viscosity of Newtonian liq
uids. If two parameters, torque, M, and difference of angular velocities, ω ω
o i
− ,
are measured (in practice, as a general rule, one of the velocities equals zero),
viscosity can be calculated as a measure of the ratio of these parameters:
η
ω ω
=
KM
o i
−
[5.27]
where Kis a geometrical factor, i.e., the value determinedby geometrical sizes of
an instrument used for measurement. In a cylinder  cylinder rotational
viscometer
A. Ya. Malkin 139
K=
R R
4 HR R
o
2
i
2
i
2
o
2
−
π
When a rotational viscometer is used as an instrument for absolute measure
ments, the value of a geometrical factor, K, is found fromthe sizes of instrument
elements. If this apparatus is used for comparative measurement, the value of K
is found froma calibration experiment in which the torque and angular velocity
are measured for a liquid with known viscosity. Then Eq 5.27 is used in order to
find the Kvalue for the instrument.
The rotation of a cylinder in an infinite volume is an interesting limiting case
(R
o
∴χ4 ∞). Velocity distribution in flow of a Newtonian liquid in an infinite vol
ume is expressed by the equation
V =
R
r
2
ω
[5.28]
whereωis an angular velocity of cylinder rotation, Ra radius of cylinder, and r a
current radius (distance fromthe axis of a rotating cylinder). Eq 5.28 shows that
velocity decreases to zero “at infinity”, i.e., sufficiently far froma rotating cylin
der.
The torque applied to rotate a cylinder in an infinite volume is calculated ac
cording to the equation
M= 4 HR
2
πηω
Rotationof a cylinder inanunlimited volume is a model case used inmany real
situations when a size of a rotating body is much smaller than the size of a sam
ple (for example, rotation of a screw propeller in a sea).
Numerous experiments were carried out to confirm theoretical predictions on
the relationship of torque, rate of rotation, and geometrical sizes of rotating bod
ies. All of them demonstrated good correlation between theory and experimen
tal results in limits of a laminar flow. It proves the basic assumptions used in
building the theory, and in particular, the validity of the NewtonStokes rheo
logical equation for many real liquids.
140 Rheological viscous fluids
It is interesting to investigate the situation when a gap between cylinders is
filled with viscoplastic liquid. Let the shear stress at an inner cylinder be calcu
lated in usual manner as
σ
π
i
i
=
M
2 R H
[5.29]
and shear stress at an outer cylinder is
σ σ α
o i
1
=
It is evident that
σ σ
o i
<
The whole volume of a material flows if
σ σ
o y
>
i.e., stress at any point of a material exceeds the yield point. If this condition is
not valid, we have a situation when a solid (nonfluid) layer exists near an outer
cylinder (up to the value of a radius where shear stress becomes equal to yield
stress), and this solid layer rotates together with an outer cylinder.
(ii) Flow under pressure. Let us assume that both boundary surfaces are mo
tionless and flow between planes along the yaxis is provoked by the pressure
gradient gradP= ∆P/L. The shear stress profile is given by Eq 5.16, which can be
written as
σ σ =
P
L
y
w
−
∆
[5.30]
It is convenient to drawa coordinate systeminsucha manner that the plane
y = 0 would coincide with a middle section of a gap (plane of symmetry). Then co
ordinates of the boundary parallel planes are +H/2 and H/2. It is easy to under
stand that the flow through a channel is symmetrical and
A. Ya. Malkin 141
dv
dy
= 0 at y = 0
i.e., the velocity profile has a maximumat the middle plane (or at y = 0). If dV/dy
· 0, then shear stress also equals zero, which means that
σ
w
=
P
L
∆
[5.31]
The shear stresses, shown in Figure 5.3,
have a linear profile. The shear stress is zero
at the axis of a stream, and maximal at the
wall, as calculated from Eq 5.31.
The last two conclusions (existence of the
maximum in velocity profile at the axis of a
stream and linear profile of shear stresses)
are valid for any liquid. The velocity profile
must be different because linear change in
shear stress leads to linear change of shear
rate only for a Newtonian liquid; in all other
cases, velocity profiles for “rheological” liq
uids will be nonlinear.
Figure 5.4 demonstrates three typical situations:
• velocity profiles for Newtonian liquid (a)
• nonNewtonian liquid (b)
• viscoplastic liquid (c).
The first case (flow of a Newtonian liquid) is the simplest case. The linear pro
file of stress is automatically reflected by a linear profile of shear rate and thus a
parabolic profile of velocity. It looks like this:
V(y) =
H
8
P
L
[1 (2 ) ]
2
2
− −
η
β
∆
[5.32]
The “minus” signbefore the righthandside of this equationshows that flowoc
curs in a direction opposite to the gradient of pressure, andβis a dimensionless
distance from the axis of a channel: β = y/H.
142 Rheological viscous fluids
Figure 5.3. Profile of shear stresses
in flow between two parallel planes
under pressure gradient.
The volumetric output in the flowof a Newtonian liquid under a pressure gra
dient is expressed in the following manner:
Q=
BH
12
P
L
3
−
η
∆
[5.33]
Shear rate profile and the value of the shear rate at the wall (maximal shear
rate) can be calculated as often required in applications, especially in the theory
of viscometry:
& γ
o
2
=
6Q
BH
[5.34]
It is useful to introduce a value of the average velocity, V
o
, determined as
V =
Q
BH
o
i.e., volumetric output divided by the area of the crosssection. Then
V =
H
12
P
L
o
2
−
η
∆
A. Ya. Malkin 143
Figure 5.4. Velocity profiles for Newtonian (a), nonNewtonian (b), and viscoplastic (c) liquids in
flow under pressure.
It is interesting to note that the maximal velocity at the axis of a channel, V
max
,
equals
V =
3
2
V
max o
Now, we can write the equation for the velocity distribution in a dimensionless
form
V
V
V
=
3
2
[1 (2 ) ]
*
o
2
≡ − β [5.35]
where V
*
is dimensionless velocity.
Finally, if pressure, which must be created to produce some average velocity of
a stream in a plane tube of the length, L, is of interest, it can be calculated as
∆P= 12 V
L
H
o
2
η [5.36]
Let us carry out a similar analysis for nonNewtonian liquids. First of all, we
can see that nonlinear relationship between shear stress and shear rate results
inthe rate of shear profile, thoughits value at the axis is zero as before. Thenthe
velocity profile becomes nonparabolic (but with the maximum at the axis of a
stream).
Let us assume that the rheological properties of a liquid are expressed by a
power law often used in the theory of polymer processing. This relationship can
be written as follows
σ = K
dV
dy
dV
dy
n1






where K and n are constants of the rheological equation and the segment writ
ten before rate of shear can be treated as apparent viscosity depending on shear
rate.
144 Rheological viscous fluids
Such “power” liquid velocity profile is expressed by the equation
V(y) =
n
n+ 1
 P
KL
H
2
1 2
1
n
n+1
n
n+1
n
∆ 
.
`
,

.
`
,
−

.
`
,
β
[5.37]
where β = y/H as before.
Maximal velocity (at the axis of a channel) is
V =
n
n+ 1
H
2
 P
KL
max
n+1
n
1
n

.
`
,

.
`
,
∆
and it is easy to find an average velocity
V =
1+ n
1+ 2n
V
o max
For n = 1, these relationships take the form of the abovewritten expressions
for a Newtonian liquid; therefore, the rheological effects cause modification in
the velocity profile, with all the evident consequences of this phenomenon.
Shear rate profile is easily calculated as a derivative of velocity. Two points are
of particular interest. The first is the zero value at the axis, although it does not
give useful information, because shear stress is also zero, giving a quite trivial
relationship between these variables. The second point is much more interest
ing. It is a point at the wall. We can calculate shear stress at this point according
to Eq 5.31 to find shear rate at the wall as
& γ
w
2
=
2(2n+ 1)Q
nBH
[5.38]
Shear rate at a wall, in flow of a “power” liquid, can be expressed through the
corresponding value of a Newtonian liquid
& & γ γ
w o
=
2n+ 1
3n
A. Ya. Malkin 145
where the value & γ
o
is calculated from Eq 5.34.
It is thenpossible to construct a flowcurve “pointbypoint”, changing volumet
ric output or pressure gradient andthus changing shear rate andshear stress.
The relationship between pressure drop and volumetric output in flow of a
“power” liquid is given by:
∆P= 2 LB
2n+ 1
n
K
Q
H
n+1
n
n
2n+1

.
`
,
[5.39]
It is evident that the last equation can be written as
∆P= K Q
n
n
[5.40]
where K
n
is the geometrical factor which is evidently calculated as
K = 2
2n+ 1
n
LB
H
n
n+1
n
2n+1

.
`
,
It is worth mentioning that the powertype relationship between pressure gra
dient and volume output reflects the power law for the relationship between
shear stress and shear rate. For the Newtonian liquid, the same relationship is
also true and n = 1, i.e., the linear relationship exists between volume output
and pressure gradient.
Let us now discuss the main peculiarities of flow of viscoplastic liquid in a
plane channel under pressure. If the shear stress at the wall, calculated fromEq
5.31, is lower than the yield stress, no movement through a channel occurs, and
the material behaves like a solid body. If shear stress at the wall and layers near
the wall exceed the yield point, then flow becomes possible in this layer but not
inthe central zone of a channel, and the velocity profile appears as showninFig
ure 5.4c.
(iii) Superposition. Insome applications (for example, intheoretical analysis of
processing of polymeric materials in extruders), it is important to understand
velocity profiles, when flow is generated by superposition of drag due to the
movement of a boundary plane and pressure gradient, and observe superposi
tion of effects discussed above.
146 Rheological viscous fluids
The general picture, illustrating velocity profiles, is shown in Figure 5.5. The
middle picture shows a pure drag flow. The left picture illustrates a very inter
esting situation when an exit is closed so that the net output is zero. In this case,
the areas between velocity profile and a vertical (zero) line are equal on positive
and negative sides. It means that output created by drag of a boundary plane is
compensated by negative (or “back”) flowunder pressure. The right picture rep
resents typical superposition of drag and pressure streams oriented in the same
direction. The existence of the drag component of flowis proven by the nonzero
value of velocity at the upper boundary plane.
Now, let us analyze an analytical expression for velocity profiles in superposi
tion of drag and pressure flow. Such analysis is easy for a Newtonian liquid be
cause we can simply summarize velocity profiles for both components of a
stream. The result of calculations in dimensionless variables is as follows:
V(y)
V
=
3 (1 )H
6 V
P
L
w
3
w
β β β
η
− − ∆
[5.41]
where β = y/H is a dimensionless coordinate, as before.
It is quite evident that Eq 5.41 contains two members. The first is a reflection
of drag flow, and the second represents flow under a pressure gradient. The
same is true for integral characteristics of flow, i.e., volumetric output:
A. Ya. Malkin 147
Figure 5.5. Velocity profiles in flowof a Newtonian liquid between two parallel planes when there
is superposition of drag and flow under pressure: (a) exit closed; (b) pure drag flow; (c) superposi
tion of drag and pressure flow.
Q=
V H
2
H
12
P
L
w
3
−
η
∆
[5.42]
(the width of a channel, B, is omitted from both members of Eq 5.42).
Again, we see that volume output consists of two components: the first is re
lated to drag flow, and the second originates from existence of a pressure gradi
ent along a channel.
It is especially interesting to separate the case of zero output represented by
the left picture in Figure 5.5. If Q= 0, we can calculate the pressure created by a
movement of a boundary plane. This pressure is
∆P=
6V
H
L
w
2
η
The structure of this equation demonstrates that the pressure created is pro
portional to the viscosity of a liquid (i.e., high pressures can appear only for
highly viscous liquids) and velocity of a moving boundary plane.
We can introduce a value of volume output due to pressure gradient, Q
P
, and
volume output due to drag, Q
D
. Then, a dimensionless ratio is a measure of mu
tual inputs of pressure and drag:
ξ
η
≡
Q
Q
=
H
6 V
P
L
P
D
2
w
∆
[5.43]
Two particular cases are of primary interest:
at ξ = 1, output is zero (the exit is closed)
at ξ = 0, there is a pure drag flow and pressure gradient is absent.
All other cases reflect superposition of both factors and their relative “weight”
is determined by the value of ξ.
If a flowing liquid is characterized by nonNewtonian properties, the general
physical idea of superposition of drag and pressure flow remains valid. More
over, characteristic pictures drawn in Figure 5.5 are also valid. That is why in
discussion of Figure 5.5 we did not mention what “rheological” kind of a liquid it
represents. Depending on rheological character of liquid, the analytical expres
sions for velocity profiles and output must be modified. Besides, the method of
calculation of net output, as an arithmetic sumof drag and pressure outputs cal
148 Rheological viscous fluids
culated separately, which has been used above, may become invalid. There is no
simple method for calculating inputs of both components. It appears necessary
to solve the balance equations for any newtype of rheological liquid and analyze
a solution on an individual basis. Such solutions are not of general value, which
is the main point in discussion of superposition of drag and pressure flow of
nonNewtonian liquids.
5.5.3 FLOW THROUGH STRAIGHT TUBES UNDER PRESSURE
Flow through a straight channel (tube), with arbitrarily chosen crosssection,
under pressure gradient, is a classical hydrodynamic problem. It is often called
the Poisseuille problem, though Poisseuille himself studied flow in channels
with round crosssection only. The importance of this problem is determined by
the fact that flow in straight tubes is a very realistic model for numerous appli
cations, such as transport of oil and oil products, pumping water in city net
works, and many others.
The example of flow through straight tubes under a pressure gradient has
been already discussed in the case of flow between two parallel plates
(Figure 5.4).This discussion concentrates on the situation when the crosssec
tion of a tube is circular with a radius, R.
We can immediately state that the relationship between pressure gradient
and volume output is expressed by Eq 5.40 and for a Newtonian liquid (n = 1)
Q= K P ∆
The value of the geometrical factor, K, depends on the formof a crosssection of
a channel. In flow of a Newtonian liquid through a channel, with a round
crosssection, the geometrical factor is
K=
R
8 L
4
π
η
and the solution of the Poisseuille problem is the very wellknown
HagenPoisseuille equation:
Q=
R
8
 P
L
4
π
η
∆
[5.44]
A. Ya. Malkin 149
Anequationfor a velocity profile inthe flowof a Newtonianliquidis givenby
v(r) =
1
4
P
L
(R r )
2 2
η
∆
− [5.45]
where r is a current radius.
The average velocity V
o
is
V
Q
R
=
R
8
 P
L
o
2
2
≡
π η
∆
Since the pressure gradient is proportional to flowoutput, it is easy to write the
velocity distribution along a radius through output:
v(r) =
2Q
R
(R r )
4
2 2
π
−
The velocity profile is parabolic and the maximal velocity, V
max
, at the axis of a
tube is
V =
PR
4 L
=
2Q
R
= 2V
max
2
2
o
∆
η π
[5.46]
Velocity profile can be written in dimensionless form
v
V
=
v
2V
= (1 )
max o
2
−β
where β = r/R is a dimensionless radius of a tube.
The velocity profile is known and thus it is possible to calculate shear rate dis
tribution along a radius. Two points are of particular interest. The first of them
is quite evident: velocity profile is symmetrical and shear rate at the axis is zero.
The second point is a position at the wall of a channel. The shear rate at the wall
is
& γ
π
w,N
3
=
4Q
R
[5.47]
150 Rheological viscous fluids
Shear stress distribution along a radius is the same as in a parallel plate con
figuration, i.e., linear:
σ σ β =
P
2L
(R r) = (1 )
w
∆
− − [5.48]
where σ
w
is shear stress at the wall of a tube:
σ
w
=
PR
2L
∆
[5.49]
It is evident that the ratio of shear stress to shear rate calculated at the same
point (at the wall of a channel) is indeed the viscosity based on Newton  Stokes
definition:
η=
PR
8QL
4
∆
[5.50]
In fact, Eq 5.50 is the Hagen  Poisseuille equation, which is widely used for
measuring viscosity of various liquids determinedfromthe ratio of pressure gra
dient to volume output if geometrical sizes of a channel (its radius and length)
are known.
Linear relationship between output and pressure gradient, in flowof a Newto
nian liquid through straight tubes, is of a general nature, only geometrical fac
tor is varying. For example, if a cross section of a tube is not round but elliptical
the geometrical factor is
K =
1
4 L
a b
a + b
el
3 3
2 2
η
π
where a and b are semiaxes of an ellipsis.
It is quite natural that, if a = b the factor K
el
becomes the geometrical factor for
a round tube. It is also interesting that, if a → ∞ and b = H/2, we arrive at the
geometrical factor for flow of a Newtonian liquid between two parallel plates.
The next example is flowthrough a gap between two coaxial round tubes along
the axis. Let the radii of the tubes be R
o
for an outer tube and R
i
for an inner tube
A. Ya. Malkin 151
and β = R
i
/R
o
. The geometrical factor for a Newtonian liquid, in this case, is
K =
R
8 L
(1 )
(1 )
ln(1 )
c
o
4
4
2 2
π
η
β
β
β
− −
−
]
]
]
]
Again, we arrive at the boundary cases: if R
i
=0, we returnto the flowthrougha
tube with a round crosssection. And if the gap is very narrow and β→ 1, we ar
rive at flow between two parallel plates.
The geometrical factors are also calculated and their analytical forms are
knownfor channels withdifferent regular crosssections, for example for rectan
gular or triangle channel, for a channel formed by two round tubes with shifted
axes, and so on. These solutions are represented by infinite sums of different
structure and they will not be reproduced here only because they are too bulky.
Moreover analytical expressions of geometrical factors can be obtained for a
channel of an arbitrary crosssection without special problems by means of com
puter calculations. They also can be found experimentally for model or real
channels.
The situation becomes more complicated for nonNewtonian liquids because
the geometrical factor depends onthe kindof a rheological equationof state used
for calculation. As an example, let us discuss relationships for a “power” liquid
bearing in mind that Eq 5.40 is always valid.
In flow of a “power” liquid through a straight channel with a round crosssec
tion, we have the following velocity profile
v(r) =
n
n+ 1
R
P
2L
K 1
r
R
1+n
n
1
n
1
n
1+n
n
∆ 
.
`
,

.
`
,
]
]
]
]
Then,
V =
n
n+ 1
R K
P
2L
max
1 + n
n

1
n
1
n
∆ 
.
`
,
152 Rheological viscous fluids
and the average velocity is related to the maximal velocity by
V =
1+ n
3+ n
V
o max
If n = 1, the last equation transits to the above discussed equation for a Newto
nianliquid. This is also true for all relationships obtainedfor a “power” liquid.
Volume output  vs  pressure gradient for a “power” liquid is calculated from
the following equation:
Q=
n
1+ 3n
R K
P
2L
1
1 + 3n

1
n
1
n
∆ 
.
`
,
The equation used in the theory of capillary viscometry is an expression for
shear rate at the wall:
& & γ γ
w w, N
=
3+ n
4
[5.51]
i.e., wall shear rate for a “power” liquid is related to the corresponding value cal
culated for a Newtonian liquid in accordance to Eq 5.47.
Apparent viscosity of a nonNewtonian liquid, η, can be found as a ratio of
shear stress to shear rate at the same point  at the wall:
η
π
=
1
2(3+ n)
P
L
R
Q
4
∆
[5.52]
In the case of n = 1, this equation transits to the Hagen  Poisseuille equation
and apparent viscosity is constant. For a nonNewtonian liquid, it is not true be
cause apparent viscosity becomes shear rate or pressure dependent. In this case
Eq 5.52 allows one to construct the flowcurve, i.e., to find the dependence of ap
parent viscosity and shear rate, calculated by volume output, or shear stress,
calculated from pressure gradient.
Analogous equations can be obtained for different nonNewtonian liquids but
in real practice only “power” liquid flowcurves are used for applications. In this
case, Eq 5.40 is used as a basic equation, and the geometrical factors are calcu
A. Ya. Malkin 153
lated or found experimentally for channels of a different crosssection.
The other, very important case, thoroughly investigated by many authors, is a
flow of viscoplastic, nonNewtonian liquid.
Let us write onedimensional rheological equationof state of a viscoplastic liq
uid, similar to Chapter 4 (Eq 4.7), in the form
& γ
η
σ σ =
1
( )
p
y
−
which has correct meaning when σ σ >
y
.
The flow of a viscoplastic liquid through a tube occurs only when shear stress
at the wall (maximal shear stress existing ina material) exceeds the yieldstress,
i.e., when
σ σ
w y
>
If this condition is fulfilled, a flow occurs in a layer adjacent to wall. It is clear
that, at an axis of a symmetrical tube, the shear stress is zero and there is cen
tral zone near the axis where stresses are always lower than the yield stress. It
means that, in movement of a viscoplastic liquid through a tube, there is
twozone pattern: flowing layer near a wall and nondeformable pluglike zone
around an axis. This pattern has been already shown in Figure 5.4c, and it is the
same for any crosssection of a straight channel.
Volume output in movement of a viscoplastic liquid is a sum of two compo
nents  flow through a nearwall ring and plug movement at the central zone.
The solution of the hydrodynamic problem for a viscoplastic liquid is known as
the Buckingham  Reiner equation
Q=
R
8
P
L
1
4
3
+
1
3
4
p
4
π
η
β β
∆
−
]
]
]
[5.53]
where
β
σ
σ
=
w
y
154 Rheological viscous fluids
The equation is written in the form of the classical Hagen  Poisseuille equa
tion (item in the front of the square brackets) and a correction term (inside the
square brackets), which reflects the effect of plasticity.
If we have the movement of a viscoplastic liquid, under sufficiently high pres
sure gradient with developed flowzone, for example if β< 0.5, then it is possible
to use the approximate form of Eq 5.53:
Q
R
8
1
4
3
4
p
≈ −

.
`
,
π
η
β
The structure of Eq 5.53 allows one to rewrite it with variables used for a New
tonian liquid using shear stress and shear rate values related to a wall:
& γ
σ
η
β β
w, N
w
p
4
= 1
4
3
+
1
3
−
]
]
]
[5.54]
where as before
σ γ
π
η
w w, N
4
p
=
PR
2L
; =
R
8
∆
&
Another form of the last equation for β < 0.5 is
σ σ η γ
w y p w, N
=
4
3
+ &
If the real shear rate at a wall, in movement of a viscoplastic liquid, is to be
found, it can be done using the following equation
& & γ γ
β
β β
w, VP w, N
4
=
3(1 )
3 4 +
−
−
−
[5.55]
Values of shear stress and shear rate measured at the same point (at a wall)
can be used for constructing flow curves of viscoplastic liquids.
A. Ya. Malkin 155
Many other solutions of different hydrodynamic problems are known for
viscoplastic liquids. Their main feature is the existence of a nondeformable
plug in a zone where stresses are lower than the yield stress in onedimensional
flows or its invariant analogue in multidimensional deformation pattern. Ana
lytical solutions of these hydrodynamic problems are used for various applica
tions related to practical use of such materials, for example transportation of
greases through tubes or their work in bearings, designing pumping devices for
paints, displacement of sealants, and so on.
5.5.4 PENETRATION OF A CYLINDER INTO A VISCOUS MEDIUM
The penetration of a symmetrical hard (solid) body into a viscous medium is a
model of numerous real applications, for example, the technology of metal roll
ing, stamping of plastic materials, moving auger ina soil or oil layer, andso on.
It is possible to separate three main cases:
• flowof a liquidbetweentwo coaxial cylinders along their walls  Figure 5.6a
• penetration of a solid body into a vessel with a bottom  Figure 5.6b
• penetration of a solid body into an infinite ”sea"  Figure 5.6c.
The general similarity of all three cases is that they are all drag flows originat
ing from the movement of solid borders. In this sense they are close to the drag
flow discussed above. It is especially evident in the first case, because if the gap
between cylinders is small we arrive at flow of a liquid between two parallel
planes. However, if the gap is not small we meet with a new problem.
The velocity distribution in flow of a Newtonian liquid between two cylinders
as in Figure 5.6c is described by the equation
v(r) =
(V + V )lnr R
lnR R
V
i o i
o i
i
− [5.56]
Certainly it is very easy to change this equation for changing directions of
movement of both cylinders or to analyze the case when one of the cylinders is
not moving ( V
o
or V
i
is zero).
Let us discuss the situation shown in Figure 5.6b. In the general case, the
shape of bothbodies (a penetrating body anda vessel) canbe quite arbitrary, i.e.,
radii of an inner cylinder, R
i
, and an outer cylinder, R
o
, are functions of the coor
dinate z, directed along the axis of cylinders: R
i
(z) and R
o
(z). Then, two cases are
possible: a penetrating body has a sharp top or a flat bottom of the radius R. In
156 Rheological viscous fluids
the latter case R
i
(z = 0) = R.
The main parameter of interest in this problemis the resistance force F which
must be applied in order to push a penetrating body into a viscous liquid. This
value consists of two components:
• due to viscous friction along the side surface of a penetrating body, F
f
; it can
be found if we know shear stresses on the surface;
• due to pressure acting onto the penetrating body F
p
; this value is also a sum
of two components  pressure on the side surface of a penetrating body, F
p,1
,
andpressure acting onthe flat bottom, F
p,2.
The first component is absent if R
i
is constant, i.e., if a penetrating body is a straight cylinder of a constant ra
dius, R. The second component is absent if a penetrating body has a sharp
top and R = 0.
Let us assume that the gap between a penetrating body and an outer vessel is
small, so we cantreat the flowas unidimensional. The velocity of a movement of
a penetrant is V and is assumed to be constant. At the initial moment, a pene
trating body touches a surface, thenit begins to sink into a liquid forcing a liquid
up to a gap. The height of a layer is H, and the distance from the top of a pene
trating body to the bottomof a vessel is l, both values are changing in time, pro
portional to sinking of a body into a liquid.
A. Ya. Malkin 157
Figure 5.6. Different types of penetration of a cylinder into a liquid: (a) relative movement of two
coaxial cylinders; (b) penetration of a cylinder into a vessel (both having arbitrary but symmetric
shape); (c) penetration of a cylinder into an unlimited volume.
All conclusions concerning resistance force canbe made if we knowtwo charac
teristics of the flow velocity and pressure distributions. Certainly both depend
on rheological properties of a liquid. Let us analyze the problemfor a Newtonian
liquid.
The general solution for the velocity distribution in flow between cylinders is
known. It looks rather bulky though, in fact, it is not too complicated:
V (r) = V
lnr R
lnR R
+
1
4
p
z
r
R lnr R R lnr R
lnR
z
o
i o
2 i
2
o o
2
i
−
∂
∂
−
−
η
i o
R
]
]
]
]
[5.57]
where r is a current radius.
The pressure gradient enters Eq 5.57 and it must be found independently. The
pressure distribution is
p(z) = 4 V
dz
(R + R )lnR R (R R )
H
z
o
2
i
2
o i o
2
i
2
−
− −
∫
η [5.58]
Now, we can calculate all components of the resistance force.
Inorder to findF
f
, we needto knowshear stresses at the solidsurface. They are
found from
σ η =
dv
dr
, at r = R (z)
z
i






Then we can calculate shear friction component of resistance
F = 2 V
(R R )dz
(R + R )lnR R (R R )
f
0
H
o
2
i
2
o
2
i
2
o i o
2
i
2
πη
∫
−
− −
[5.59]
The integral can be easily calculated if both functions R
i
(z) and R
o
(z) are
known, and they are knownbecause inanalysis of any real problem, the shape of
a penetrating body and a vessel are known.
The component of the resistance, originated frompressure acting onto the side
surface of a solid body F
p,1
, is calculated as
158 Rheological viscous fluids
F = 2 p(z)R (z)
dR
dz
dz
p,1
0
H
i
i
π
∫
[5.60]
where p(z) is pressure distribution given by Eq 5.58.
Certainly, it is seenthat F
p,1
=0 if dR
i
(z)/dz =0, as has beenmentionedabove.
The component of the resistance, due to pressure acting on the bottomof a pen
etrating body is calculated as
F =
3
2
V
R
l
+ 4 VR
dz
(R + R )lnR R (R R
p,2
4
3
2
0
H
o
2
i
2
o i o
2
i
2
πη πη
∫
− − )
[5.61]
where R is a radius of a flat bottom.
If R = 0 (a penetrating body has a sharp top) this component of the resistance
force is absent.
An interesting and important case is a narrow gap between two cylinders:
δ = R R << R
o i i
−
In this case all above written formulas can be simplified and the approximate
relationships are as follows.
Resistance due to shear friction force:
F 6 V
R
dz
f
0
H
i
2
2
≈
∫
πη
δ
[5.62]
Resistance due to pressure on the side surface:
F 12 V
R dz
R
dR
dz
dz
p,1
0
H
0
H
i
3
i
i
≈
]
]
]
∫ ∫
πη
δ
[5.63]
Resistance due to pressure on the bottom of a penetrating body:
F V
3
2
R
l
+ 6R
R dz
p,2
4
3
2
0
H
i
3
≈
]
]
]
∫
πη
δ
[5.64]
A. Ya. Malkin 159
It is rather evident that the relative impact of all these components on a net re
sistance force differs, and it depends the depthof penetrationof a body into a liq
uid besides all other factors concerned. It can be analyzed quantitatively based
on Eqs 6.62  6.64, but it is clear that the role of pressure acting on a bottomof a
penetrating body increases when the body approaches the bottom of a vessel.
Let us consider the situation when a round cylinder is penetrating into a cylin
drical vessel. In this case we have: R
i
= R = const and R
o
= const. Let us assume
that R
o
 R<<R, i.e., the gapbetweencylinders is narrow. Inthis case F
p,1
=0. It is
also reasonable to think that F
f
< F
p,2
. Then, the following equation allows one to
calculate the resistance force
F V
3
2
R
l
+
6R H
4
3
3
3
≈

.
`
,
πη
δ
[5.65]
We can introduce the depth of penetration, ξ, and obtain
H 1+
R
2
≈

.
`
,
δ
ξ
The final expression for the resistance force is as follows
F
3
2
VR
R
(l )
+
2R
3
o
3 4
≈
−
]
]
]
πη
ξ
ξ
δ
[5.66]
This solution of the hydrodynamic problem under discussion can be used for
designing dampers, calculating forces in hot stamping of metals and plastics
whena puncheonis pressing ina liquidmediumduring a technological process.
If an outer cylinder is absent, it describes penetration of a solid body into infi
nite liquid medium, as in Figure 5.6c. We may analyze this problemfor the case
whena penetrating body is a thinflat plane (Figure 5.7). The velocity of penetra
tion is constant and equal to V. In this case, on the contrary to the above dis
cussed, the flow of a liquid is twodimensional and the component of velocity v
z
depends on two coordinates y and z.
The solution of the problem regarding the velocity distribution in a liquid me
dium is known:
160 Rheological viscous fluids
v (y,z) = V 1 Erf
y
2
V
z
z
1
2
− −

.
`
,
¹
'
¹
¹
¹
¹
'
¹
¹
¹
ηρ
[5.67]
where ρ is density of a liquid and Erf(x) is an
error function determined by the equation
Erf(x) =
2
e d
1
2
2
0
x

π
α
α
∫
Shear stresses, at the surface of a plane, are
σ η
η
π ρ
w
z
y =0
=
v
y
= V
V
z
1
2
∂
∂







.
`
,
Now, the final expression for the resistance force, F, for a thin plane penetrat
ing into a viscous Newtonian liquid and the depth of penetration, H, can be
found. For a plane of the width B, considering two sides of plane, the following
equation is valid:
F= 4B
HV
3
1
2
ηρ
π

.
`
,
[5.68]
The situation included in Figure 5.6c  penetration of a cylinder into an infinite
medium canalso be analyzed theoretically. The analytical solutionof this prob
lem is known and can be found in textbooks on hydrodynamics.
It is worth saying that the last problem is very important for penetration of a
tube into different media, for example in oil industry. In this case, the soil can be
treated as a Newtonian liquid and the known solutions can be applied to this
problem only as the first approximation. In fact, real rheological properties of a
medium must be taken into consideration, i.e., those of a soil and an oil layer.
A. Ya. Malkin 161
Figure 5.7. Penetration of a thin
plane into a liquid medium.
The solution of this problemcan be reached if a proper description of the rheo
logical properties of a medium is used, followed by the same formal operations
which have been utilized in analyzing the problem for a Newtonian liquid.
5.5.5 RESISTANCE TO ROTATION OF A THIN DISK IN A LIQUID
Let a thin disk rotate in a viscous fluid around its axis. The width of a disc is
muchsmaller thanits radius, R, whichallows one to neglect the edge effects (the
socalled von Karman problem).
5
It is necessary to find the resistance to a ro
tation as a function of its speed and R. This problem is a model for many real
technological operations, for example, for mixing a liquid by rotationof anagita
tor.
The torque, M, is determined for a Newtonian liquid as
M= 4 r
V
z
dr
0
R
2
z=0
πη
ϕ
∫
∂
∂





 [5.69]
where zcoordinate axis is oriented normal to the surface of a disc, rcoordinate
axis coincides with the radius of a disc, and V
ϕ
is a circular component of the ve
locity vector.
Detailedcalculations of the rate of shear fieldandthena torque give the follow
ing result
( )
M= 11.8R
4 3
1
4
ηρΩ [5.70]
where Ω is the rate of rotation, and ρ density.
Inthe theory of mixing (agitation), the dimensionless coefficient of viscous fric
tion, C
mf
, is usually used. Then, it is easy to demonstrate that the dependence of
this coefficient on the dimensionless characteristic Reynolds Number is
C =
1.8
Re
mf
0.5
[5.71]
where the Reynolds Number for the problemunder discussionis expressedas
162 Rheological viscous fluids
Re =
R
2
Ωρ
η
The numerical value of the coefficient in Eq 5.71 is a result of approximate so
lution of the hydrodynamic problem. In fact, it can be rather different if we take
into account the edge effect and some other details. Nevertheless, Eq 5.71 is a
good approximation and gives results close to experimental data. Meanwhile,
two limitations must be remembered:
• Eq 5.71 is valid for laminar flow only
• Eq 5.71 is found for a Newtonian liquid.
Transition to turbulent flowchanges the law
of resistance. It can be representative if we
consider the dependence of the dimensionless
coefficient of viscous friction on the Reynolds
Number in logarithmic coordinates (Figure
5.8). At Re < Re* (in laminar flow), Eq 5.71 is
obeyed. In transition to the turbulent zone at
Re > Re*, where Re* is the critical value of the
Reynolds Number corresponding to lami
nartoturbulent transition, the viscous resis
tance has larger effect than predicted by this
equation (dotted line in the range of Re >Re*).
Figure 5.8 resembles Figure 4.18, and indeed
it represents the same phenomenon of the de
pendence of hydrodynamic resistance on the
rate of flow.
For nonNewtonian flow, Eq 5.71 needs to be modified without changing its
structure. The expression for the Reynolds Number reflects nonNewtonian
properties of a liquid, as in the case of a powertype liquid discussed above. The
value of the numerical coefficient in Eq 5.71 can be different than the 1.8 ob
tained for a Newtonian liquid. The exact value depends on the rheological prop
erties of a real liquid and can be found theoretically and/or experimentally for a
real situation of torque resistance during rotation of a disk in various “rheologi
cal” liquids.
A. Ya. Malkin 163
Figure 5.8. Dependence of the co
efficient of viscous friction in rota
tionof a thindisc inside a liquidon
the Reynolds Number: transition
froma laminar (I) to turbulent (II)
zone.
5.5.6 CONVERGING (DIVERGING) FLOWS
Converging (or diverging) flows take place when a crosssection of a channel is
changing along its axis. Flowin channels with changing crosssection (diffusors
 channels with decreasing crosssection, and confusors  channels with increas
ing crosssections) is a rather standardsituationindifferent technological appa
ratuses and transportation pipes. Therefore, this problem was thoroughly
studied theoretically, and exact solutions are knownfor Newtonianliquids only.
In all other cases, solutions for “rheological” liquids are found by numerical
methods.
The size of a crosssection can be quite arbitrary, but two cases are of main in
terest to model real situations. That is:
• flow through a cone channel
• flow in a channel formed by two flat inclined planes.
Basic diagram of flow in a flat
diffusor
6
is shown in Figure 5.9, where
definitions of coordinate axes are given
in a cylindrical coordinate system.
We can assume that there is only one
nonzero component of velocity, which
is radial velocity, as shown in Figure
5.9. Velocity equals zero at the walls,
and the velocity profile is symmetrical
to the plane α = 0.
The solution of a hydrodynamic prob
lem of a Newtonian liquid flow is
known, andone canfindit intextbooks
on hydrodynamics. It is expressed in the
form of elliptic functions, and velocity
profile and pressure gradient can be cal
culated for any particular case. For
nonNewtonian liquids, a solution of the problem of converging (or diverging)
flow can be analyzed by computer methods only.
One of the interesting results of the theory of diverging flowof a Newtonianliq
uid in a diffusor is proof of the fact that a pure converging flowcan exist only for
sufficiently small angles, α
o
, or
164 Rheological viscous fluids
Figure 5.9. Scheme of flow between two
flat inclined planes. The cylindrical coor
dinate system is shown.
α α
o max
< [5.72]
where2
max
α is some critical value of the angle between plates and it depends on
the Reynolds number, Re.
For the problem under discussion
Re =
Q
B
=
r V
B
o
ρ
η
α
η
where Q is volume output, B width of a channel (in the direction perpendicular
to the plane of a drawing), V
o
average velocity, and r and α are current coordi
nates.
If the condition 5.72 is not obeyed, zones with backstreams appear. These
zones can exist near walls, or zones with direct and back streams can alternate,
and the number of such zones depends on Re.
The exact analytical solution for α
max
is known, though it is rather complex.
For Re > 1 (in the limits of laminar flow), a simple approximate relationship
takes place:
α
max
10.2
Re
≈
i.e., the value of α
max
is small.
In the situation when an angle α
o
is very small, velocity profile can be calcu
lated as
V(r, ) =
3
2
Q
B r
1
o o
2
α
α
α
α
−

.
`
,
]
]
]
]
[5.73]
So, the velocity profile at each crosssection (determined for r = const) is para
bolic, and Eq 5.73 is very similar to the wellknown HavenPoisseuille solution
for flowof a Newtonian liquid through a flat tube. It is quite an expected result,
but it is important to emphasize that it is valid only for very small values of α
o
,
i.e., for slightly diverging flat tubes. Inthe opposite case, velocity profiles appear
A. Ya. Malkin 165
to be nonparabolic.
Let us consider some peculiarities of flow in converging channels (confusors).
Again, simple analysis can be done for Re > 1. In this case, we come to the inter
esting result: velocity profile appears almost flat for the main part of crosssec
tionof a channel, andonly near walls is there anabrupt decrease of velocity upto
zero at the walls. It means that viscous resistance occurs in a very thin (narrow)
layer near the walls. According to the theory, the size of this layer is proportional
to (Re)
1/2
. This fact is the base for the theory of a boundary layer which explores
the general ideas: effects of viscous resistance to floware important only at short
distances from the solid surfaces, and then viscous effects are negligible.
The general approach to the theory of flow in conical diverging (converging)
channels is very similar to the analysis of flow in a flat channel with changing
cross section. It is convenient to analyze the
problem in a spherical coordinate system,
where the originis at the apex of a cone (Fig
ure 5.10). The flowis symmetrical inrespect
to the axis of a cone and two components of
velocity V
r
and V
α
are present, where r is ra
dial, and α angular coordinates.
Even for a Newtonian liquid, the solutions
of hydrodynamic (balance) equations are
known in the form of a series only. In the
first approximation (when only the older
member of the series is preserved), pressure
distribution in flow through a round cone
channel is represented in the following
manner:
p p =
Q(1 3 )
(1 ) (2 + 1)
1
r
1
r
o
2
o
2
o o
3 3
−
−
−
−

.
`
,
η γ
π γ γ
[5.74]
where γ α α ·cos and is a current angle calculated from an axis of a cone,
γ α
o o
= cos , whereα
o
is an angle between a solid wall of a cone and its axis, r, is a
current radius of a diffusor, r
o
is a radius of the edge cross section, p
o
is pressure
in this section, and Q is a volume output.
166 Rheological viscous fluids
Figure 5.10. Flow in a cone channel.
The spherical coordinate system is
shown.
The preservation of the first member of a series for p(r) is valid for viscous liq
uids when their viscosity is sufficiently high. This is true for many liquids, such
as polymer melts or crude oils, but for lowviscosity liquids, it is necessary to uti
lize the full solution of a problem, which can be found in standard textbooks on
hydrodynamics.
The pressure drop is proportional to the volumetric output and this is a feature
typical for Newtonian liquids. In a general case, we can think that the relation
shipbetweenvolumetric output andpressure drop, for a Newtonianliquid, must
be linear and can be expressed by an equation
Q= K
P ∆
η
where ∆P is the pressure drop providing volumetric output, Q, for a Newtonian
liquid having viscosity, η, and K is the geometrical factor depending on the size
of a channel.
The exact expression for K is rather complex, and the first approximation can
be found fromEq 5.74. However, one can find a simpler equation for K, based on
the following arguments. If we consider a conical channel as a sum of round
channels of the length dl, with changing radius, r, it seems reasonable to sum
marize pressure drops, dp, for all segments of a channel. This values can be cal
culated fromthe HagenPoisseuille equation, resulting in the expression for ∆P.
Along the way we shall find the following result
K =
3
8L
R R
R R R + R
1
3
2
3
1
2
1
2
2
2
2
2
π
+

.
`
,
where R
1
is a radius of a conical channel at the entrance, R
2
is a radius of a coni
cal channel at the exit, and Lis the lengthof a channel (betweenradii R
1
and R
2
).
However, this result is not adequate for the rigorous solution expressed by the
known series or even its first approximation represented by Eq 5.74.
We can expect that for “rheological” liquids, the relationship between pressure
drop and volumetric output will appear nonlinear. Indeed, for a powertype liq
uid, this relationship is expected to be
A. Ya. Malkin 167
Q= K ( P)
(n)
n
∆
where the geometrical factor, K
(n)
, can be calculated theoretically from the solu
tionof a balance equation. Again, it seems that calculating K
(n)
andsummarizing
pressure drop in cylindrical segments of a channel of the length, dl, can lead to
inadequate results.
If a liquid is viscoplastic, the central zone will be motionless, as in flow in cy
lindrical channels, because shear stress at the axis is absent, and stresses are
less than yield stress near the axis. It is clear that the radius of this pluglike
zone is changing along its length.
Avery interesting, special case is a flowof an elastic liquid (i.e., a liquid able to
store large deformation in the course of flow) through a conical channel. Let the
radius of a conical channel be changing along its length from R
1
to R
2
. Then,
bearing inmind that the volume output is constant, we cancalculate average ve
locities at entrance and exit sections V
o,1
and V
o,2
. They are
V =
Q
R
; V =
Q
R
o,1
1
2
o,2
2
2
π π
It means that the flow in a conical channel is accelerating and an extensional
gradient of velocities appears. The gradient of velocity equals
& ε =
V V
L
o,1 o,2
−
and the extension ratio is
λ =
R
R
1
2
2

.
`
,
Flowof an elastic liquid in a conical channel leads to uniaxial extension, and its
characteristics can be found using the last two equations.
Extension of an elastic liquid in its flowthrough a conical channel can be effec
tively used for creation of an orientation which is fixed beyond the exit section of
168 Rheological viscous fluids
a channel. This idea is a basis for the technological operation which is utilized in
production of highstrength and highmodulus polymeric filaments.
5.5.7 MOVEMENT OF A BALL THROUGH A VISCOUS FLUID
The hydrodynamic problem of calculating the force required for a sphere to
move through a viscous liquid was first analyzed by Stokes, and is known as the
Stokes problem.
7
Two cases are possible and are
considered intheory. The first is a
steady movement of a solid body
in unlimited (infinite) volume
(see Figure 5.11a). In this case,
solid walls are absent or placed so
far from a moving ball that their
influence is negligible. The sec
ond case is a movement of a solid
body in a vessel (Figure 5.11b)
where the influence of walls on
the hydrodynamic situation must
be taken into account. The latter
case is close to the situation dis
cussed above, when the problem
of penetrating a symmetric body
into a symmetric vessel was ana
lyzed.
A solid ball moving through a viscous liquid is a very popular model of numer
ous real situations. The simplest of themis the process of sedimentation of solid
particles due to gravitational forces. A moving body does not need to have a
spherical shape but a defined geometrical shape instead. It is a model of various
bodies moving in a sea (submarines and many others). That is the reason why
calculationof a resistance to movement of solidbodies througha viscous liquidis
a very important problem met in different applications.
According to a wellknown solution by Stokes, the force, F
s
, necessary to sup
port the steady movement of a ball in a Newtonian liquid is calculated as
F = 6 RV
s
πη [5.75]
A. Ya. Malkin 169
Figure 5.11. Movement of a spherical ball inaninfi
nite volume (a) or inside a vessel (b).
where R is a radius of a ball (sphere), V velocity of the steady movement.
Further analysis shows that this solution is valid at low Reynolds Numbers
calculated as
Re =
2RVρ
η
where ρ is density of a liquid.
It was shownthat influence of inertial forces (i.e., transitionto situations when
Re is not small) can be analyzed using correction factors. According to
Goldstein’s calculations, the exact formula for resistance to movement of a ball,
when Re is not small, is as follows
F= F 1+
3
16
Re
19
1280
Re +
s
2
−
]
]
]
K
where F
S
is the Stokes force calculated from Eq 5.75.
It is evident that the second member in the brackets (linear correction term)
canbe neglected incomparisonwith1 whenthe Reynolds Number is of the order
of 0.1.
The movement of a ball due to gravitational forces is of special interest. In this
situation, the moving force, P, is calculated as a difference between weight of a
ball and hydrostatic flotation force:
P=
4
3
R g( )
3
s 1
π ρ ρ − [5.76]
where g is the gravitation constant, ρ
s
density of a moving solid body, ρ
1
density
of a liquid.
In the steady movement, F
s
calculated from Eq 5.75 and P calculated from
Eq 5.76 are equal, and then we can find the velocity of steady movement
V =
2
9
gR
2 s 1
ρ ρ
η
−
[5.77]
170 Rheological viscous fluids
If velocity is measured and densities of a solid ball and liquid are known, Eq
5.77 can be used to determine viscosity of a Newtonian liquid. It is quite evident
that
η ρ ρ =
2
9
gR
V
( )
2
s 1
− [5.78]
This formula can be used only with the following limitations:
• it is valid for steady movement of a ball
• it is possible to neglect the influence of walls of a vessel
• rheological properties of a liquid are described by the NewtonStokes Law
• movement of a ball is rather slow and Re < 0.1.
If movement of a ball is not very slow, and inertial effects must be taken into
consideration, the equation for viscosity calculation must be modified:
η η
ρ
ρ ρ
= 1
27
16
V
gR
s
2
1
s 1
−
−
]
]
]
where η
s
is viscosity, calculated according to the Stokes formula, Eq. 5.77. The
second member in the brackets is a correction factor for inertial effects.
A very special modification of the Stokes problem is related to the situation
whena moving ball is not a solidbut liquidandits viscosity is η
o
. Theoretical cal
culations show that in this case the velocity of steady movement can be calcu
lated as
9
V =
2
3
g( )R +
2 + 3
o
1
2 o
o
ρ ρ
η
η η
η η
−
[5.79]
where ρ
o
is density of a liquid ball, and η
o
its viscosity.
It is evident that if η
o
→ ∞, we may apply Eq 5.77 for a solid ball moving in a
viscous liquid. Another limiting case is connected with the assumption that
η η
o
<< , for example, the case of a gas bubble in a viscous liquid. Then
V =
1
3
g R
2
−
ρ
η
[5.80]
A. Ya. Malkin 171
The “minus" sign, in the last equation, shows that a gas bubble moves in a direc
tion opposite to the positive coordinate axis, i.e., up rather than down as in for
mer cases.
Both Eqs 5.79 and 5.80 can be used for practical applications in different tech
nological problems related to liquidliquid separation, degassing, and so on.
Eq 5.77 is a linear relationshipbetweenvelocity andreciprocal viscosity. Then,
for a Newtonian liquid, the resistance to movement of a ball can be written as
F= K V η [5.81]
where K is a geometrical factor. For a spherical body
K= 6 R π
For solid bodies of various shapes, Eq 5.81 seems to stay valid but the problem
of calculation of the geometrical factor is quite independent and requires sepa
rate theoretical or experimental determination. Sometimes, the same equation,
as for a sphere, is used, and in such case, Rmeans some geometrical parameter.
For example, if a moving body is a thindisk of a radius, R, and a disc is moving in
the direction perpendicular to its plane, then
R=
8a
3π
If this disk is moving along its plane, then
R=
16a
9π
Other situations (for example, ellipsoids, cylinders, and so on, moving in a New
tonian liquid) also can be investigated by methods of theoretical hydrodynamics
which allow us to establish values of the geometrical factor. Nevertheless, in
practice, especially for bodies of complicated geometrical shape (for example,
submarines), it is preferable and more reliable to find values of K experimen
tally or on the basis of some empirical formulas.
172 Rheological viscous fluids
It is also useful to have a formula for calculationof stress field around a moving
ball. The complete stress distributioncanbe calculatedbut the solutionis rather
complex. The most important value is the maximum shear stress. It acts at the
surface of a ball and can be found as
σ ρ ρ
max s 1
=
R
3
( )g − [5.82]
Now, let us consider what happens if a ball moves, not in infinite liquid space,
but in a vessel where the influence of its walls cannot be neglected; for example,
if a ball is falling in a cylindrical tube.
Theoretical analysis shows that in this case, Eq 5.77 for viscosity must be mod
ified by adding a correction factor. According to the wellknown calculations by
FaxenLadenburg, viscosity of a Newtonian liquid is expressed as
8
η η = 1 2.104
R
R
+ 2.09
R
R
0.95
R
R
s
o o
2
o
−

.
`
,

.
`
,
−

.
`
,
]
]
]
]
4
where R
o
is a radius of an outer cylinder (tube) along which a ball is moving and
η
s
is viscosity calculated from the Stokes equation (5.77).
It is easily seen that corrections become comparable with 1 at (R/R
o
) > 0.01.
Then, in many practical cases, the introduction of corrections is necessary, and
only in some special cases, is it reasonable to neglect the influence of the walls of
a vessel.
If a liquid is nonNewtonian, the resistance force can be found by numerical so
lution of hydrodynamic equations with an appropriate constitutive equation.
Simple final expressions are absent, but we can think that, for a “power law” liq
uid, the dependence of the resistance to movement, F, at velocity, V, can be ex
pressed by the power equation
F= K V
(n)
n
where K
(n)
is a geometrical factor, as before, and n an exponent in a power law(of
the rheological equation of state).
A. Ya. Malkin 173
In application to shearrate dependent viscosity, results of determination of
apparent viscosity depend on a driving force, or shear stress. In this case the fol
lowing procedure is useful: it is necessary to make measurements and calculate
apparent viscosity at different shear stresses and then extrapolate experimen
tal data to “zero” conditions (zero shear stress or zero shear rate). This limiting
“zero” apparent viscosity can be treated as a quite reliable value of maximum
Newtonian viscosity.
The method of extrapolation can be rather arbitrary. For example, we can as
sume that inthe range of relatively lowshear stress, the dependence of apparent
viscosity on shear stress is expressed as
η
η
σ
=
1+ A
o
2
where η
o
is maximum (“zeroshear”) Newtonian viscosity and A is constant.
Then, Newtonianviscosity is found by extrapolationof η σ ( ) dependence toσ = 0
in coordinates η σ
1 2
− . Shear stress is calculated from Eq 5.82.
Other methods of extrapolation, to σ = 0 in various coordinate systems used to
determine “zeroshear” Newtonianviscosity, canalso be foundinthe literature.
If a liquid is viscoplastic, then it can flow (i.e, a ball can move through such a
medium) only if maximal shear stress calculated from Eq 5.82 exceeds yield
stress. In the opposite case, a medium behaves as a solid and it is irrelevant to
consider resistance to the movement of a ball.
5.5.8 COMPRESSION OF A LIQUID BETWEEN TWO PARALLEL DISKS
Let a Newtonian liquid be placed between two parallel round plates (discs).
The liquid layer is compressed because of bringing the plates together
(Figure 5.12). This problem was first analyzed by Reynolds.
10
There are peculiarities of flow under discussion, as follows:
• It is reasonable to assume that the radial component of velocity dominates,
i.e.,
v << v
z r
174 Rheological viscous fluids
and besides
∂
∂
∂
∂
v
r
<<
v
z
r z
(orientation of the axes is shown
in Figure 5.12).
• Inertial forces are neglected, i.e., we
analyze the case of relatively low
values of the Reynolds Number.
• The flowis symmetrical inrespect to
the axis passing through the center
of the disks.
Two different basic cases are of pri
mary interest:
• flowinducedby the preset constant velocity of the upper plate moving down:
at z = h, v
z
= V = const, and v
r
= 0
where h is the distance between parallel plates.
• flow generated by a constant force applied to the upper plate.
Let the velocity of the upper plate, V, be known. Then, we wouldlike to know
• time dependence of the force which resists approaching the disks and must
be applied in order to support movement
• velocity and pressure profiles.
First, let us consider the situation when a liquid completely fills the space be
tween disks and when they are approaching each other the surplus of a liquid
squeezes out the gap and does not take part in further consideration, so the vol
ume of a liquid in the gap decreases with time.
It is evident that, at V = const, the distance between disks, h, is linearly de
creasing with time because
v =
dh
dt
A. Ya. Malkin 175
Figure 5.12. Compression of a liquid layer
between two parallel plates (discs) squeez
ing out a liquid from the gap.
The solution of the problem under discussion for velocity distribution is
v =
1
2
p
r
(z hz)
r
2
η
∂
∂
− [5.83]
and we need to know pressure distribution
∂
∂
−
p
r
=
6 v
h
r
3
η
[5.84]
finally we have
v
V
= 3 ( )
r
2
α γ γ − [5.85]
where dimensionless sizes are used:
α γ =
r
h;
=
z
h
Pressure distribution along the radius is
p = p +
3 V
h R
(1 )
o
3 2
2
η
ζ − [5.86]
where ζ = r/R is a dimensionless radius, and p
o
is pressure at the outer free sur
face, at r = R.
The integral of p(r) along the radius gives the full force, F, required to create
movement with constant velocity
F=
3 VR
3h
4
3
πη
[5.87]
The resistance to approaching plates increases with h
3
, and h grows (at
V · const) linear to time. These results showwhy it is so difficult to squeeze out a
176 Rheological viscous fluids
liquid from narrow gaps pressing solid boundary
surfaces: whenthe distance betweensurfaces, h, be
comes very small, the force grows rapidly up to un
limitedly highvalues, and a very thinfilmof a liquid
always stays in a gap.
Let us now discuss the situation when the size of
discs is large and a liquid stays in the gap between
discs (Figure 5.13), i.e., we wish to compress a small
liquiddrop. Inthis case the conditionof constant liq
uid volume is valid
π π R h = R h
o
2
o
2
where R
o
andh
o
are initial radius andheight of a liquiddroplet, respectively, and
R and h are current (timedependent) values of the droplet sizes.
In this situation the resistance force is calculated as
F=
3 VR h
h
o
4
o
2
5
πη
and, in the case of constant volume of a liquid droplet, the resistance force in
creases with h
5
, i.e., even faster than in the former case, when a liquid is
squeezed out the gap.
If a liquid placed between plates is nonNewtonian, it is not very difficult to
make all necessary calculations and find all analogous formulas for velocity and
pressure distribution, resistance force, and so on. The formof these formulas de
pends on the accepted rheological equation of state of a liquid.
However, if a liquid is not only viscous but viscoelastic (see Chapter 7), the gen
eral solution does not exist.
When a compressing force, but not a velocity, is preset, the movement of an up
per plate becomes slower and slower when discs are approaching each other be
cause of increasing resistance to flow in a narrow gap, which again
demonstrates how difficult it is to squeeze out a liquid from a narrow gap.
The results of theoretical calculations discussed above are widely used in the
rubber industry. There are some standard methods to characterize rawmateri
als by their behavior in compression between parallel plates (in socalled com
pression plastometers). These methods are particularly convenient for such
highly viscous liquids as raw rubbers.
A. Ya. Malkin 177
Figure 5.13. Compressing
of a liquid between two
parallel plates when a liq
uid stays in the gap.
Perhaps the main application of the flow of a liquid between compressing
plates is related to understanding the performance characteristics of greases in
sliding bearings, and this problemsuccessfully models the main peculiarities of
grease performance. However, industrial greases are very often viscoplastic
and/or viscoelastic liquids, and when quantitative characteristics of their per
formance are of interest, it requires rigorous analysis of the complete hydrody
namic problem with an appropriate rheological equation of state. In this case,
taking into account plasticity of a liquid is especially important, because it is
easy to imagine that a thin layer of a solidlike material will stay in the gap be
tween solid surfaces, and this circumstance prevents the contact of sliding bod
ies.
5.5.9 HYDRODYNAMICS OF ROLLING
The situation shown in Figure
5.14 is a model of many indus
trial applications including roll
ing of metal slabs, stretching
wires, processing of plastics and
rubber compounds, and so on.
That is why this model was in
vestigated for different rheologi
cal liquids. In order to give an
idea about main peculiarities of
the model, we shall cite some re
sults primarily related to flow of
a Newtonian liquid.
11
Let a flat slab (strip) of a viscous
or viscoplastic liquid pass
through the gap between two
rolls, withthe driving force for this movement being the rotationof the rolls. The
initial widthof a strip is 2Hand the widthof a gap is 2h, Hand hbeing muchless
than the radius of the rolls, R. The main characteristic parameter of the stream
is the outstripping factor, δ, determined as
δ =
Q Q
Q
o
o
−
178 Rheological viscous fluids
Figure 5.14. Model of rolling.
where Q
o
is an apparent quantity of a material which would pass through the
gap if a material is solidlike and moves with the circumferential velocity of the
rolls:
Q = 2 RBh
o
ω
where B is the length of the rolls, ωis angular velocity (frequency of rotation),
andQis a real quantity of a material passing througha gapbetweenthe rolls:
Q= 2 v dy
0
h
x
∫
[5.88]
v
x
is a velocity component directed along the xaxis.
Theoretical calculations give the following approximate expression for the
δfactor in rolling of a Newtonian liquid:
δ
α
α
αβ α α =
1
+ 1
1+ 2 1
5
6
+
1
3
2
−
−

.
`
,
]
]
]
[5.89]
whereα =H/handβ=h/Rare dimensionless geometrical parameters andβ<< 1.
It appears that the δfactor is completely determined by geometrical sizes of
the apparatus used. This is true for a Newtonian liquid. But in fact (and experi
ments confirmit) theδfactor depends onrheological properties of liquid and can
be distinguished from the values calculated using Eq 5.89.
Theory also gives formulas for pressure distribution along the surface of rolls,
net force, F, which moves rolls apart, and power consumption in roll rotation.
For a Newtonian liquid, F can be expressed by a linear relationship:
F= Kηω
where K is a geometrical factor, calculated via α β , , and R.
There are a lot of publications devoted to calculations of the dependencies of
the force, F, on geometrical sizes of an apparatus and rheological properties of a
material for nonNewtonianand viscoplastic liquids. The results were obtained
by either analytical or finite element analysis methods and canbe used to design
A. Ya. Malkin 179
industrial equipment and determine its technological characteristics. The final
formulas and applied guidelines for calculations can be found elsewhere.
12
One
important fact worth mentioning: for “rheological” liquids, the dependence of F
on angular velocity is not linear as for a Newtonian liquid; this result is quite
analogous to other abovediscussed conclusions for flows of different types when
we transit from Newtonian to nonNewtonian liquids.
5.5.10 FLOW IN A LUBRICANT LAYER
This is a rather special but very important
case of flow, modelling deformations of a
grease in a gap, not in compression (as dis
cussed in previous section), but in a tangential
movement. In fact, it is a development of a the
ory of flow between two round cylinders when
eccentricity (shift in position of axes of cylin
ders) exists, as shown in Figure 5.15. It is a
model of a radial bearing with a lubricant and
shift of a bob (rotating shaft) fromthe common
axis can be initiated by a radial force.
Theoretical calculations
10,13
give the angular
distribution of pressure. If we integrate this
distributionthroughanangle, we arrive at the mainresult of the theory of lubri
cation. This result is a proof that an additional radial supporting force appears,
and this force prevents shift of a bob fromthe common axis and favors its stabili
zation in rotation. This force, F, is calculated as
F=
6 SR V
(1+ 2 )( 1)
i i
2
2 2 2
1
2
η α
δ α α −
[5.90]
where R
i
is a radius of a bob (inner cylinder or a rotating shaft), V
i
is a speed at
the surface of a bob (V
i
=ωR
i
), ωis frequency of rotation, S is the surface of a bear
ing (S=2πR
i
L), Lis the lengthof a bob, δ is the average gapbetweencylinders
(δ = R
o
 R
i
), R
o
is a radius of an outer cylinder, α is dimensionless eccentricity:
α δ ε = and ε is eccentricity, i.e., the distance between axes of inner and outer
cylinders.
180 Rheological viscous fluids
Figure 5.15. Flowina lubricating
layer between two eccentric
cylinders.
It is also possible to find the torque, M, for a rotating bob. The resulting equa
tion is
M=
SV R 2 (2+ )
(1+ 2 )( 1)
i i
2
2 2
1
2
η
δ
α α
α α −
[5.91]
There is a correspondence between eccentricity and two main parameters: sup
porting force, F, and torque, M. Eq 5.90 can be rewritten as
F
6 SV R
=
2
i i
δ
η
γ
where
γ
α
α α
=
(1+ 2 )( 1)
2
2 2
1
2
−
is a function of eccentricity.
Then, it can be easily demonstrated that at low values of γ (i.e., at low radial
forces or  what is more important  at high velocities of rotation) α grows unlim
itedly (i.e., eccentricity, ε, becomes very
small). It means that an increase in rate of
rotation really results in stabilization of the
position of a bob close to the axis of an outer
cylinder.
The limiting situation corresponds to the
case of α → ∞. This case can be modeled as
shown in Figure 5.16: an inclined plate is
moving relative to a flat surface. Change of
the distance between plates is characterized
by the linear relationship
h= h 1+ k
x
a
o

.
`
,
A. Ya. Malkin 181
Figure 5.16. Flow between a flat
surface and a sliding inclined plate.
where the meaning of notations a, x, h, and h
o
is given in Figure 5.16 and k char
acterizes the inclination of the upper plate. Coordinate axes are also shown in
this Figure.
Sliding of a flat plate is a limiting case of the full theory, whichcorresponds to a
slightly forced or very quickly rotating shaft when the eccentricity is small. In
this situation, a supporting force, F, also appears, and it is calculated as
F=
6 VBa
k h
ln(1+ k)
2k
2+ k
2
2
o
2
η
−
]
]
]
[5.92]
where B is the size of plates in the direction perpendicular to the plane of the
drawing.
It is easy to prove that Ppasses througha maximumat k≈1.2, andat this value
of k, maximal value of the supporting force is
F 0.16 V
a B
h
max
2
o
2
≈ η
It is also possible to find the resistance force, P, which acts against the direc
tion of movement (sliding) of an upper plate
P=
VBa
kh
4ln(1+ k)
6k
2+ k
2
o
η
−
]
]
]
[5.93]
Thus, due to the appearance of a supporting force, F, a lubricating layer can re
sist pressure and this is the physical reason why a lubricant works.
Though the classical theory of lubrication was developed for a Newtonian liq
uid, in fact, the majority of lubricants used in industry are “rheological” liquids
and the whole theoretical structure built for a Newtonian liquid must be re
peated for any other liquid if quantitative results are expected. It is relatively
simple for a pure viscous liquid, but introduction of elasticity leads to many new
effects which depend on real properties of a medium (or, in other words, on the
rheological model used). Therefore no general solution exists, but the main idea
concerning the existence of a supporting force ina lubricant layer is valid for any
liquid.
182 Rheological viscous fluids
5.6 CONCLUDING REMARKS
In real life we meet with liquids very often. In some cases we cannot be quite
sure whether a material is a liquid or not. This is true, for example, for such sub
stances as resins (especially at lowtemperatures), bitumen, semiliquid glasses,
glues, and so on. Therefore, we need a rigorous definitionof a liquid. Suchdefini
tioncanbe basedonthe idea that liquidis a material whichflows, i.e., its defor
mations are irreversible, and for a pure liquid, no elastic deformation can
exist. Moreover, liquid is a substance which can flow at infinitesimally small
stresses. However, this definition requires estimation of a time factor, because
development of deformation proceeds in time and always there is a danger that
an experimenter did not have enough time to observe any deformations at all.
That is why it is correct to consider liquidlike behavior of matter “froman ex
perimental point of view”. If relaxation takes place much quicker than defor
mation (or stress) is measured, it is reasonable to treat this substance as a
liquid.
Another approach to an idea of flowof a liquid is related to the concept of dissi
pation of energy supplied to create flow: work done for deformation of a liquid
is completely converted to heat (dissipates), which is opposite to deformation of
solids, where work is completely stored, or to viscoelastic media, where work is
partly stored.
The position intermediate between solids and liquids is occupied by
viscoplastic bodies: they cannot flowup to some limit of stress (yieldstress)
and at low stress they behave as solidlike bodies. But at stress higher than the
yield stress, such media flow, i.e., they behave as typical liquids. The level of the
yield stress can be very low (infinitesimally small), and that is why, in practice,
it is not always possible to distinguish between pure viscous and viscoplastic
media.
Rheological equation of state (constitutive equation) for any liquid can be for
mulated either in terms of relationship between invariants of stress and rate of
deformation tensors or as energy dissipated as a function of invariants of these
tensors. In this case, the criterion of yielding for a viscoplastic liquid must be
also established in terms of invariants of the stress tensor.
One of the fundamental concepts in rheology is an idea of a Newtonian (or
Newton  Stokes) liquid. This is the simplest linear liquid, i.e., liquid for
which linear relationships between components of stress and rate of deforma
A. Ya. Malkin 183
tion tensors exist. The coefficient for this linear relationship is viscosity (or
Newtonian viscosity), and according to the definition, viscosity of Newtonian
liquids is a material characteristic of a liquid which does not depend on condi
tions of flow (i.e., on stresses or rates of deformation).
Viscosity of a Newtonian liquid can be measured at different geometrical
schemes of deformations. As a general rule, the termviscosity is related to shear
flow, and this coefficient is a constant of proportionality between shear stress
and rate of shear. All other coefficients of viscosity are related to this value. For
example, a coefficient between normal stress and rate of extension measured in
unidimensional stretching, called Trouton viscosity, is equal to the
threefoldvalue of the shear viscosity of this liquid. It means that shear viscosity
is a unique material parameter of a Newtonian liquid.
However, if a liquid is anisotropic (as liquid crystals), some independent vis
cosities exist even in a linear model of a liquid, and viscosity appears to be a ten
sor value by itself.
Many real liquids are nonNewtonian. It means that their apparent coeffi
cient of viscosity, determined as a ratio of shear stress to shear rate of deforma
tions, depends on conditions of flow. Various mathematical models of
nonNewtonian flow have been proposed, discussed in literature, and used for
solving applied problems. Among them, one of the most popular is the socalled
“power” liquid. This liquid is characterized by power dependence of shear
stress on shear rate.
Different mathematical equations are proposed for viscoplastic liquids, too.
The simplest of them is the Bingham model. In this model, shear rate is pro
portional to the difference betweencurrent shear stress andthe yieldstress. But
apparent viscosity of the Bingham model is not constant, but rather, is a de
creasing function of shear stress.
Rheological models of liquids are used by for comparison of different liquids.
This comparison can be done for two levels:
• different liquids can be distinguished by the constitutive equation which de
scribes their flow properties in the best way
• liquids of the same rheological type canbe distinguished by the values of ma
terial constants which enter these equations as numerical coefficients.
The main field of application for rheological equations of state (constitutive
equations) is in solving hydrodynamic problems, which are described by
balance equations with appropriate boundary conditions.
184 Rheological viscous fluids
To solve a hydrodynamic problem means:
• to find space distribution of stresses, velocities, and pressures for a certain
volume determined by solid boundaries
• to establish relationship between integral force and kinematic parameters
of flow, such as pressure drop and output in flow through channels (inner
problems) or resistance force and velocity for movement of a solid body
through a liquid (outer problems).
There is a great variety of hydrodynamic problems because the number of pos
sible configurations of channels through which liquids flow and solid bodies
moving inside a liquid is unlimited. But some situations are very typical and are
widelyused for modelling real technological and engineering situations. These
are: plane unidimensional flow, flow through tubes with different constants
and changing crosssection, movement of solid bodies in a liquid, compression of
a liquid layer between planes, rotating rolls, and so on.
These are only a fewexamples, and certainly many other hydrodynamic situa
tions exist. For any of them, the hydrodynamic problemcanbe solved by analyti
cal and/or computer methods.
If any of these hydrodynamic situations is analyzed for a Newtonian liquid, we
canexpect that a linear relationship betweenintegral force (or torque) and kine
matic parameters (velocities) takes place. For nonNewtonian liquids, analo
gous relationships are nonlinear. In the case of viscoplastic media, motionless
zones appear in areas where stresses do not exceed yield stress of a material.
Some hydrodynamic problems for a Newtonian liquid can be solved analyti
cally; others require applying approximate or computer methods to find solu
tions. For nonNewtonian liquids, mathematics becomes (as a general rule) too
complex to find solution in an analytical formand the methods of computational
analysis are used.
5.7 REFERENCES
1. V. G. Kulichikhin and A. Ya. Malkin, Vysokomol. Soed., 21A, 1407 (1979).
2. R. S. Rivlin, Proc. Roy. Soc., A193, 260 (1948).
3. I. Braun and M. Reiner, Quart. J. Mech. Appl. Math., 5, 42 (1952).
4. M. Couette, Ann. chim. phys., 21, 433 (1890).
5. Th. Kármán, Zeitschr. für angew. Math. Mech., 1, 244 (1921).
6. G. Hamal, Jahresber. Deutsch. Math. Ver., 25, 34 (1916).
7. G.G. Stokes, Trans. Camb. Phyl. Soc., 9, 8 (1851).
8. R. Landenburg, Ann. der Phys., 22, 288 (1907); 23, 447 (1907)
9. T. Rybczynski, Bull. Acad. Sci. Cracovie, 40 (1911); J. Hadamar, Comp. Pendus, 152,
A. Ya. Malkin 185
1735 (1911).
10. O. Reynolds, Phys. Trans., 177, 157 (1886).
11. I. V. Meshcherski, Repts. First Petrograd. Polytechn. Inst., 28 (1919).
12. R. E. Gaskell, J. Appl. Mech., 17, 334 (1950); N. Tokita and J. L. White, J. Appl.
Polym. Sci., 10, 1011 (1966); I. Brazinsky, J. Appl. Polym. Sci., 14, 2771 (1970).
13. Lord Rayleigh, Phys. Mag., 35, 1 (1918).
186 Rheological viscous fluids
6
ELASTIC SOLIDS
6.1 DEFINITIONS
The concept of an elastic solid is an idealization of the real behavior of numer
ous materials. Some of them are close to this model − for example, steel and
stone. Others are rather far fromthis ideal model, but in some applications they
can also be treated as elastic solids − for example, wood, rubber, and concrete.
These examples showthat the elastic solid is in fact a concept of behavior rather
than a particular material. On the other hand, the same material can behave as
a solidlike or liquidlike material, depending on the timescale of observation.
Consequently, the type of rheological behavior is determined by the Deborah
Number, i.e., the ratio of inner and outer timescales.
The basic idea of an elastic solid has already been formulated in Chapter 4.
The elastic solids are materials which completely store work of their deforma
tion and return energy after removal of the outer forces.
Another approach to the idea of elastic solids can also be advanced. If elastic
solids are treated as materials with an unambiguous relationship between
stresses and deformations, i.e., if we know the stress field, we know the space
distribution of deformations, and vice versa.
The main point in both concepts is absence of time or timeeffects. If deforma
tion is timedependent (in a permanent stress field), it is always a characteristic
feature of viscous (or dissipative) behavior of matter, though it can be combined
with elasticity.
A. Ya. Malkin 187
The next step in formulating the rheological model of an elastic solid, i.e., in
writing its rheological equationof state (or constitutive equation), is a transition
fromcomponents of stress and deformation tensors observed in any experiment
dealing with invariant formulation. It can be an expression for elastic potential
(stored energy) as a function of invariants of stress or deformation tensor or
both. It can also be a relationship between invariants of stress and deformation
tensors. Both approaches work in formulating rheological equation of state, and
the result can be reformulated from the energy concept to the components of
stressvsdeformation tensors.
This transition is based on a fundamental expression for elastic potential
(stored energy):
dW = d
i j
ij ij ∑ ∑
σ ε [6.1]
Continuing, we arrive at the following evident formula for the stress compo
nents calculated from an elastic potential
σ
ε
ij
ij
=
W ∂
∂
[6.2]
and if we know W as a function of deformations, then components of the stress
tensor can be easily calculated from Eq 6.2.
It is also important to have a method of conversion fromthe stressvsdeforma
tion relationship, written in invariants, to the elastic potential function. W can
be written as a function of three invariants:
W = W(E
1
, E
2
, E
3
)
where E
1
, E
2
, and E
3
are invariants of the tensor of large deformations.
Then using the ordinary rule of differentiating complex functions, we have
σ
ε ε
ij
ij
k=1
3
k
k
ij
=
W
=
W
E
E ∂
∂
∂
∂
∂
∂
∑
[6.3]
188 Elastic solids
The last equation gives an answer to the problemformulated above: indeed, if a
functionW(E
1
, E
2
, E
3
) is known, we cancalculate components of the stress tensor
from Eq 6.3.
6.2 HOOKEAN ELASTIC MATERIAL
The initial formulation of the concept of the Hookean elastic material has been
given for uniaxial extension by Eq 1.2.
σ ε
E
= E
where E is the elastic (Young) modulus.
Sometimes a constant reciprocal to the elastic modulus is also used. This con
stant is called compliance, I:
I =
1
E
or
ε σ = I
E
Analogous relationships can be written for other geometrical schemes of defor
mation. For bulk (volume) compression, we have
ε
v
=
1
B
p
where ε
v
is a relative change of volume:
ε
v
V
V
·
∆
p is hydrostatic pressure and B is bulk modulus of compressibility.
Linear elastic behavior in shear is expressed by the equation
A. Ya. Malkin 189
ε σ =
1
G
[6.4]
Here ε is shear, G is the shear modulus, and σ is tangential (shear) stress.
In Chapter 3, discussing uniaxial extension, we introduced the values of the
Young modulus, E, and the Poisson coefficient (ratio), µ. Evidently, there
are many characteristics of linear rheological behavior of a material  bulk,
shear, Young moduli, Poisson coefficient. It is also possible to think about other
types of deformations (e.g., biaxial extension), and it would be necessary to in
troduce “moduli” characterizing linear behavior of a material. Then the main
questions are:
• how to write the general rheological equation of state for such material, re
flecting its linear elastic properties indifferent modes of deformations which
would include all these relationships?
• what is a minimal number of independent characteristic constants
(“moduli”) describing all types of deformation of a material?
The first, most straightforward attempt to construct the general rheological
equationof state for a linear elastic material appears to consist of anassumption
of linear relationship between corresponding components of the stress and de
formation tensors, such as
σ ε
ij ij
= k [6.5]
where kshouldbe anuniversal constant characterizing properties of a material.
But this approach is evidently wrong. Indeed:
• experiments showthat the constant k is not universal because coefficients of
linear equations for bulk compression, extension, and shear are different
and this is not reflected in the concept of the linear relationship between cor
responding components of stress and deformation tensors
• in uniaxial extension, ε
22
andε
33
(in directions perpendicular to the line of ex
tension) are not zero because an extended body compresses in perpendicular
directions, but the components of the stress tensorσ
22
andσ
33
are absent, and
this means that there is no simple correlation between σ
ij
and σ
ij
.
Therefore, one needs to find a different form of invariant description of rheo
logical properties of a linear (Hookean) elastic material.
190 Elastic solids
The basic idea of constructing such a description is related to the fact that in
uniaxial extension, not only the form but a volume of a body changes, and these
are different and independent effects. In a more general sense, we assume that
shape (form) and bulk (volume) changes in deformation are independent phe
nomena and must be considered separately. That is why we need to introduce at
least two independent constants for complete characterization of resistance of a
material to volume changes, on one hand, and the resistance to shape changes,
on the other. This recalls the idea of splitting stress and deformation tensors
into spherical (isotropic) and deviatoric parts.
Assuming that linear relationships between spherical and deviatoric parts of
both tensors exist separately
I = kE
1 1
[6.6]
and
σ ε ′ ′
ij ij
= 2G [6.7]
where I
1
is the first invariant of the stress tensor (measure of hydrostatic pres
sure); E
1
is the first invariant of the deformation tensor (measure of relative vol
ume changes); σ′
ij
are deviatoric components of the stress tensor, ε′
ij
are
deviatoric components of the deformation tensor; and k and Gare material con
stants, the first of themcharacterizing resistance to volume and the second one,
shape changes of a material.
If we recall that hydrostatic pressure
p =
I
3
1
− [6.8]
then Eq 6.6 can be rewritten as
p = BE
1
−
where B = k/3 is the bulk modulus of elasticity. The two fundamental coeffi
cients, B and G, are sometimes called Lamé factors.
A. Ya. Malkin 191
The value of GinEq 6.7 is the shear modulus, and the coefficient 2 inEq 6.7 re
lates the formal definition of components of the deformation tensor.
We can assume that Eqs 6.6 and 6.7 are valid for any type of deformation and
that they are the invariant definition of a Hookean elastic material (body). It is
important to connect the constants in Eqs 6.6 and 6.7 with those which are di
rectly measured in a standard experiment  uniaxial extension.
Let σ
E
to be the extensional (normal) stress, and discuss the situation in the
limits of instantaneous deformations. Then, as shown in Chapter 3,
ε
σ
ε ε µε
11
E
22 33 11
=
E
; = = −
and
E = (1 2 )
E
1
E
− µ
σ
where E is the Young modulus and µ the Poisson ratio.
Hydrostatic pressure, p, in uniaxial extension is
p = = 
3
i
ii
E
−
∑
σ
σ
Then, according to Eq 6.6, we come to the equality
σ
µ
σ
E E
3
= B(1 2 )
E
−
and then we have
E= 3(1 2 )B − µ
This equation also gives us useful information because
192 Elastic solids
σ µ
σ
E
o
= 2G(1+ )
E
and as a final result
E= 2G(1+ ) µ
We cannowcalculate any pair of constants for any pair of variables, as summa
rized below.
• for known constants E and µ
B=
E
3(1 2 )
;
− µ
G=
E
2(1+ ) µ
• for known constants B and G
E=
9BG
3B+ G
; µ =
3B 2G
6B+ 2G
−
• for known G and µ
E= 2G(1+ ); µ B=
2G(1+ )
3(1 2 )
µ
µ −
• and for known E and G
B=
EG
3(3G E)
;
−
µ =
E 2G
2G
−
This set of relationships allows one to find any value of a material constant
fromtwo other values measured experimentally. It is important to note that in a
general case there are only two independent constants which need to be
measured. It is interesting to consider the expression for the bulk modulus via
constants E and µ.
It is quite evident that whenwe compress a body, its volume cannot increase; it
can only decrease or may not change at all, if a body is incompressible. It means
A. Ya. Malkin 193
that there is a principle limitation:
B 0 ≥
Then, it is also evident that E >0, and this inequality can be fulfilled only if
µ ≤ 0.5
The particular case of incompressible material is of special interest. The fact is
that for many solids
B >> G
i.e., it is much easier to change the shape of a body than its relative volume (den
sity).
Insome cases, it is reasonable to accept that B→ ∞, i.e., to think that some ma
terials are completely incompressible. It is a good model (or it is almost true) for
all liquids and rubbers. Then we have two simple relations
µ ·05 .
and
E = 3G
It means that for incompressible media there is only one independent or “free”
material constant.
Now, we can reformulate the rheological equation of state for a linear Hookean
elastic material interms of the elastic potential function. Let us consider (for the
sake of simplicity) an incompressible body. Then, E
1
= 0, and Wcan be a function
of E
2
and E
3
only.
The simplest idea is an assumption of linear relationship between W and E
2
,
i.e.,
W = BE
2
[6.9]
where B is a material constant.
194 Elastic solids
Then we can use Eq 6.9 to calculate all items entering this equation. It is easily
seen that
∂
∂
−
E
=
2
ii
ii
ε
ε (both indices are the same)
and
∂
∂
E
=
1
2
2
ij
ij
ε
ε (indices are different)
As a result we come to the linear relationship between deviatoric components
of the stress and deformation tensors as indicated by Eq 6.7, i.e., the conclusion
is equivalent to the aboveformulated concept of a Hookean elastic material. It
means that Eq 6.9 can be treated as an invariant definition of an incompressible
linear elastic body in the limits of small deformations.
Though both definitions are equivalent, it seems that Eq 6.9 does not offer any
additional advantages in comparison with the standard definition describing
the relation between components of stress and deformation tensors. However, it
is not completely true, and whenwe come to the discussionof finite (large) defor
mations of an elastic body, we may see that formulation of the rheological equa
tionof state throughanelastic potential functionis preferable because it is more
evident and elegant.
It should be useful to illustrate the real range of changes in modulus for some
typical materials:
Material Young modulus
High modulus, oriented fibers > 300 GPa
Steels 200 GPa
Copper, aluminum, and alloys 100 GPa
Stones 40  60 GPa
Engineering plastics 10 GPa
Ice 10 GPa
Wood 1  10 GPa
Leathers 1  100 MPa
Rubbers 0.1  1 MPa
Polymer and some colloid solutions 1  100 Pa
A. Ya. Malkin 195
Certainly, all values, listed for illustrative purposes, give only animpressionof
the ranges of possible values of elasticity modulus. The Young modulus can
change in the range of more than 11 decimal orders. On the contrary, the Pois
son ratio is a much more conservative value. The ordinary range of its values is
0.30.4, and only for rubbers is it very close to 0.5.
6.3 LINEAR ANISOTROPIC MATERIALS
One of the main ideas used in all the above formulations is the concept of iso
tropic properties of a material, i.e., the elastic modulus is the same, regardless of
the direction of deformation. Meanwhile, there are many elastic bodies which
are characterized by the existence of dependence of their properties onthe direc
tion of deformation. Such bodies are called anisotropic. Typical and important
representatives of anisotropic elastic bodies are monocrystals, liquid crystals,
wood, reinforced plastics; all these materials and many others possess an inher
ent regular structure which leads to anisotropy of their properties.
Rheological equation of state of such “structured” materials must reflect the
anisotropy of their properties. Then, in a general case, we can write the follow
ing expression for the components of the stress tensor:
σ ε
ij
l=1
3
m=1
3
ijlm lm
= k
∑ ∑
[6.10]
i.e., it is assumed that σ
ij
depends on all components of the deformation tensor.
The set of constants k
ijlm
are in fact components of the tensor of moduli. So rhe
ological properties of anelastic anisotropic material are represented by a tensor,
i.e., by the set of its components, not by two independent factors (Young modulus
and Poisson ratio) as was the case of an ideal Hookean solid.
Elastic potential for an anisotropic elastic material is
W = k
i,j l,m
ijlm il jm ∑ ∑
ε ε [6.11]
The tensor k
ijlm
is symmetrical, and this fact diminishes the number of inde
pendent constants characterizing elastic properties of a material. This number
in fact depends on the class of symmetry of a solid.
196 Elastic solids
It can be proven that for the highest class of symmetry, the number of inde
pendent constants is 21. This is true for crystals of triclinic symmetry. For
monoclinic crystals we have only 13 independent constants. For orthorhombic
crystals there are 9 independent constants, and for cubic crystal, only 3 inde
pendent constants (“moduli”) still remain valid. For isotropic bodies with infi
nite axes of symmetry (amorphous or polycrystal where differences of properties
are averaged because of coexistence of large number of individual anisotropic
crystals oriented statistically in space), the number of constants is only two, and
we come back to an ideal Hookean material.
6.4 LARGE ELASTIC DEFORMATIONS IN SOLIDS
Discussionof large elastic deformations insolids is the most important for rub
bers and rubber compounds because their main characteristic is their ability to
undergo large recoverable deformations. Articles made of rubbery materials
(elastomers) work in various applications in which they are subjected to a
threedimensional stress state. Meanwhile, as a general rule, the mechanical
testing of these (and other) materials is carried out in unidimensional exten
sion.
Some equations describing dependence of normal (extensional) stress on the
ratio of extension has been already brought to attention in Chapter 4. Now, our
main goal is to find ways for generalizing these equations in order to have a pos
sibility to transit from the results obtained in experiment to predictions of me
chanical behavior in arbitrary geometrical schemes of deformation (or loading).
It means that the task is to formulate a rheological equation of state (constitu
tive equation) for rubbery materials in an invariant form.
An invariant form of the Hooke Law, i.e., of the linear relationship between
stresses and deformations, has been formulated above: Eq 6.9, as a linear de
pendence of an elastic potential on the second invariant of the deformation ten
sor. In the limits of the Hooke Law, it is the tensor of infinitesimal deformations.
As discussed in Chapter 3, in the case of large deformations, it is necessary to
utilize the theory of finite deformations and use some measures of large defor
mations. It is a quite natural way for the generalization of the Hooke Law,
though we must not forget the ambiguity of measures of large deformations,
which may lead to different possibilities of representation of the relationship
under discussion.
A. Ya. Malkin 197
Rubbery materials can be treated as incompressible because their Poisson ra
tio is very close to 0.5. The first invariant of the deformation tensor, in the limit
of small deformations, has the sense of volume changes (see Chapter 3), and that
is why in this limit E
1
= 0. In the range of large deformations, E
1
does not have
such a simple sense, but the condition of constant volume at deformations of any
type permits us to diminish the number of independent invariants to two, be
cause the equality
(1 + E
1
)(1 + E
2
)(1 + E
3
) = 1 [6.12]
is always valid for incompressible materials.
Then, we can exclude any invariant representing it as a function of two others.
For example, it can be the third invariant which is expressed by means of Eq
6.12 as
E =
1
(1+ E )(1+ E )
1
3
1 2
− [6.13]
Then, we canconsider a dependence of Wontwo independent variables only:
W = W(E
1
, E
2
)
As the first approximation (or as the first reasonable simple idea), let us as
sume that anelastic potential is a linear functionof the first invariant of the ten
sor of large deformations:
W = AE
1
[6.14]
Let us analyze the consequences of this supposition, i.e., Eq 6.14, for different
geometries of deformation.
Eq 6.14, in an expanded form, can be written as
W = A( + + ) = A
1
2
+
1
2
+
1
2
1 2 3
1
2
2
2
3
2
γ γ γ
λ λ λ − − −
]
]
]
198 Elastic solids
or
( )
W =
A
2
+ +
1
2
2
2
3
2
λ λ λ [6.15]
where λ
i
are principle ratios of extension.
This formula is equivalent to the linear relationship between an elastic poten
tial, W, and the first invariant, C
I
, of the Cauchy  Greentensor of large deforma
tions
W =
A
2
(C 3)
I
− [6.16]
Let us consider now the problem of threedimensional elongation of a body “at
a point” by calculating elastic potential of deformations in the principle axes.
Fromthe definition of W, it is easy to showthat elastic potential is expressed via
principle ratios of extension as
dW =
d
+
d
+
d
1
1
1
2
2
2
3
3
3
σ
λ
λ
σ
λ
λ
σ
λ
λ
We know that for incompressible materials
λ λ λ
1 2 3
1 ·
and
d( ) = 0
1 2 3
λ λ λ
Then, after some simple rearrangements, we come to the following formula for
dW:
dW = ( )
d
+ ( )
d
1 2
1
1
1 2
2
2
σ σ
λ
λ
σ σ
λ
λ
− −
A. Ya. Malkin 199
Based on Eq 6.15, we can come to the following expression for dW:
dW = A ( )
d
+ ( )
d
1
2
3
2
1
1
2
2
3
2
2
2
λ λ
λ
λ
λ λ
λ
λ
− −
]
]
]
Direct comparison of two latter formulas for dW gives the following system of
equations
σ σ λ λ
1 3 1
2
3
2
− · − A( )
[6.17]
σ σ λ λ
2 3 2
2
3
2
= A( ) − −
The last system of equations is a solution to the problem of calculation of nor
mal stresses at known principal elongations.
Certainly, this solution is not complete because we have only two separate
equations for three independent variables, σ
1
, σ
2
, andσ
3
. This result is not unex
pected because we consider deformations in an incompressible medium. The
last limitation means that, in principle, stresses can be determined as σ
ij
+ C,
where C is a constant which cannot be determined unambiguously. Superposi
tion of arbitrary hydrostatic pressure changing stress state of a medium does
not influence its deformations. As a result, the system of Eq 6.17 determines
components of the stress tensor in relation to constant C, depending on hydro
static pressure.
Therefore, the general solution in determining principle stresses in a threedi
mensional deformation state ( i.e., when deformations are known or preset) can
be written, in accordance to Eqs 6.17, in the following form:
σ λ
1 1
2
= A + C
σ λ
2 2
2
= A + C
[6.18]
σ λ
3 3
2
= A + C
where the constant C might be found if hydrostatic pressure is known before
hand.
200 Elastic solids
Now, it is possible to analyze the main cases of deformations of an elastic solid
body with rheological properties obeying Eq 6.14. It is quite evident that in uni
axial extension along the axis x
1
, we haveσ
2
= 0 andσ
3
= 0. If the elongation ratio
λ
1
along the axis x
1
is equal to λ , the condition of the constant volume of a body
under deformation results in the following relationship:
λ λ λ
2 3
= =
1
2
Then, any of the last two equations of the system [6.18] gives
C= A
1
− λ
Finally, we come to the formula for normal stress in uniaxial extension for a
material with rheological properties described by Eq 6.14:
σ λ
λ
1
2
= A
1
−

.
`
,
[6.19]
It is a wellknown equation, which was included in Chapter 4 as one of the pos
sible methods of representation of experimental data for large deformations of
elastic materials. This equation is a consequence of Eq 6.14 or a generalization
of experimental data obtained in uniaxial extension, described by Eq 6.19.
There is not much new information in these statements. They only show that
there is a possibility to apply Eq 6.14 to other modes of deformation than uniax
ial extension. Simple shear is one of the most interesting and relatively easy to
study by experimental methods. This mode of deformation can be realized by
twisting a thinwalled cylinder. In simple shear, the principal elongations are
calculated as
λ β
1
= cotan ; λ β
2
= tan ; λ
3
1 ·
and the meaning of the angle β was explained in Chapter 3.
Now, we can calculate an elastic potential
A. Ya. Malkin 201
W =
1
2
A
2
γ
where γ is a magnitude of shift.
The following equation for shear stresses is obtained
σ
γ
γ =
dW
d
= A [6.20]
In accordance with Eq 6.14, the dependence of shear stress on deformation in
shear must be linear and thus the value of the constant A in this equation has
the meaning of shear modulus. However, if a material really behaves in shear,
as predicted by Eq 6.20, its modulus of elasticity in uniaxial extension is not ex
pected to be equal to 3Aas for a Hookean solid, and in extension the dependence
of stress on deformation is nonlinear, as described by Eq 6.19.
Therefore, the following points can be made:
• shear behavior of two different kinds of material (Hookean and described by
the rheological equationof state, 6.14) canbe the same, eventhoughthey are
quite different rheological materials, as proven by the difference in their be
havior in extension. It is the proof of the thesis that investigation of
stressdeformation behavior in one mode of loading does not yet give enough
basis for estimating the type of rheological model of a material
• elastic potential (Eq 6.14) predicts nonlinear behavior of a material in ex
tension and this nonlinearity is a direct consequence of large deformations
by itself. This rheological equation of state contains only one material con
stant, which has the meaning of the shear modulus, and can be used for pre
diction of deformation behavior of a material at any mode of loading.
Elastic potential (Eq 6.9) is an invariant rheological equation of state describ
ing properties of a Hookean material and that is why it can be called the Hooke
potential.
Elastic potential in the form of Eq 6.14 was formulated in publications by
Kuhn, Guth, James, Mark, and others as a result of the molecular (kinetic) sta
tistical theory of rubbery elasticity. That is why it can be called the
KuhnGuthJamesMark potential.
The potential function (Eq 6.14) was proposed for rubbers and indeed it can be
considered as a first approximation describing deformations of rubbers in equi
librium conditions. The last limitation implies that we do not consider time ef
202 Elastic solids
fects, though effects of such kind are quite typical for rubbers and
stressvsdeformation relationships.
The idea of representation of rheological properties of solid materials via an
elastic potential functionW(C
1
, C
2
) is quite equivalent, after some formal mathe
matical transformations, to representing it as a function W(C
1
, C
1
1
), i.e., it is pos
sible to use first invariants of the CauchyGreen and Finger tensors of large
deformations. There is great freedom in varying any conceivable form of this
functioninanattempt to fit various experimental data. Formally, no limitations
in approximating a function W(C
1
, C
1
1
) exist because any of them obey the gen
eral principle of invariance. Certainly, in real practice it is desirable to search
for these approximations in the simplest possible form.
The most simple formis linear, and one of the examples of linear elastic poten
tial is given by Eq 6.14, but it contains only one argument C
1
. Then the next pos
sible approximation is a combination of linear functions in the form
W = AC
1
+BC
2
[6.21]
where A and B are material constants.
This elastic potential can be rewritten via principle of extension ratios. After
quite evident mathematical transformation, we come to the following formula:
W = G ( + + ) + G
1
+
1
+
1
1 1
2
2
2
3
2
2
1
2
2
2
3
2
λ λ λ
λ λ λ

.
`
,
[6.22]
where “new” constants, G
1
and G
2
, are expressed by “old” ones, A and B, as
G =
A B
2
; G =
B
4
1 2
−
and the final result is
W = G (C 3) + G (C 3)
1 1 2 1
1
− − [6.23]
This result confirms the abovementioned general idea about equivalence of
functions W(C
1
, C
2
) andW(C
1
, C
1
1
). Anelastic potential inthe formof Eq 6.23 was
A. Ya. Malkin 203
proposed independently and based on different concepts by Mooney and Rivlin
and is called the MooneyRivlin potential.
Let us illustrate the role of the secondterminEq 6.23 by discussing predictions
of stressdeformation dependencies for uniaxial extension and shear.
In uniaxial extension
λ λ λ λ λ
1 2 3

= ; = =
1
2
where λ is an extension ratio.
Using formulas for components of stresses discussed above, we can show that
normal stress in the direction of stretching is
σ λ
λ
λ
λ
E 1
2
2
2
= 2 G
1
+ G
1
−

.
`
,
−

.
`
,
]
]
]
[6.24]
with two other stress components absent.
Sometimes, it is more traditional to relate acting force, not to the current but to
the initial crosssection of a stretched sample. This section is λ times larger than
a current sectionandthat is why an“engineering” (or conventional) stress, σ
e
, is
σ
λ
λ
λ
e 1
2
2
= 2 G +
G 1 
.
`
,
−

.
`
,
[6.25]
The structure of Eq 6.25 demonstrates that addition of the second item in Eq
6.23 leads to the “correction” term in Eq 6.25, and if G
2
= 0, we come back to the
wellknown formula for the stress related to a onemember elastic potential
function. The difference is connected with the item 2G
2
/λ in Eq 6.25. The influ
ence of this correction can be estimated if we remember that according to the ex
perimental data, G
2
≈0.1G
1
, but addition of the second itemis of principle value,
especially considering that other relationships between both constants are not
excluded.
Let us discuss shear deformations calculated in accordance with predictions of
Eq 6.25. It is easy to show that Eq 6.25 leads to the following dependence of
shear stress, σ, on deformation, γ,
204 Elastic solids
σ γ = 2(G + G )
1 2
[6.26]
where the sum(G
1
+ G
1
) is shear modulus, and the potential (Eq 6.25), similar to
the rheological equation of state (Eq 6.23), predicts linear behavior in shear,
though it is nonlinear in extension.
Repeatedly, this is a proof that the same rheological behavior in deformations
of one type (in this case, in linear stressvsdeformation in shear) does not mean
that the type of deformation under other conditions (in the case under discus
sion  stressvsdeformation in uniaxial extension) must be the same. The result
demonstrates again that data obtained in experiments of one type cannot be a
criterion for the choice of rheological equation of state (constitutive equation)
and cannot be used for unambiguous predictions of stressvsdeformation de
pendencies in different modes of deformations.
Eqs 6.21 or 6.23 canbe formally treated as first approximations (first members
of a series) for some nonlinear functions W(C
1
, C
2
) or W(C
1
, C
1
1
). If we add some
other members, with their own material constants, we may expect to improve
correspondence between the theoretical predictions and the experimental data.
In particular, it is important for shear studies because the linear relationship in
Eq 6.26 is not a realistic result.
If linear functions (Eq 6.21 or Eq 6.23) are not sufficient, we can try to add the
quadratic member and write an expression for an elastic potential as
W = AE + BE + ME = G (C 3) + G (C 3) + G (C 3)
1 2 1
2
1 1 2 1
1
3 1
2
− − − [6.27]
where A, B, M, G
1
, G
2
, and G
3
are material constants and the latter three are ex
pressed via A, B, and M.
Based on Eq 6.27, the following formula for normal engineering stress in uni
axial extension can be derived:
σ
λ
λ λ
λ
e 1
2
3
2
2
= 2 G +
G
+ G
1 
.
`
,
−

.
`
,
[6.28]
It is evident that Eq 6.28 contains a newquadratic termwith its own material
constant in a “correction” member, compared to Eq 6.25. Certainly, three empir
ical constants allow us to fit experimental points much better than one or even
two “free” constants in Eq 6.25, and that is why Eq 6.28 approximates different
A. Ya. Malkin 205
experimental data quite satisfactorily. Moreover, Eq 6.28 predicts nonlinear
stressvsdeformation dependence in a simple shear.
The most general form of an elastic potential function is
W = K (C 3) (C 3) (C 3)
, , =0
, , 1 2 3
α β γ
α β γ
α β γ
∞
∑
− − −
where K
, , α β γ
are empirical constants and K
000
= 0 because elastic energy of an
undeformed body is assumed to be zero.
For an incompressible material, C
3
= 0, and we can obtain a simpler general
form of elastic potential:
W = K (C 3) (C 3)
, =0
, 1 2
α β
α β
α β
∞
∑
− −
Avery interesting and principle problemarises concerning the practical possi
bility of finding W as a function of invariants. The general answer to this prob
lem is that it is necessary to compare results of experiments carried out at
different geometrical schemes of loading. For example, a normal stress inuniax
ial extension for an arbitrary function W(C
1
, C
2
) can be expressed as
σ λ
λ λ
E
2
1 2
= 2
1 W
C
+
1 W
C
−

.
`
,
∂
∂
∂
∂

.
`
,
The dependence of shear stress on deformation (its measure will be written as
γ) for simple shear can be formulated as
σ =
W
C
+
W
C
1 2
∂
∂
∂
∂

.
`
,
The normal and shear stresses depend on an elastic potential function in a dif
ferent manner. Comparing dependencies of σ
E
normalizedby 2(λ
2
 λ
1
) andσ nor
malized by 2γ, the difference is evident fromcomparisonof the right sides of both
expressions, and it is possible to calculate an elastic potential function.
206 Elastic solids
Certainly, other types of fundamental experiments can also be used to find an
elastic potential function W(C
1
, C
2
) but it is essential that at least two different
geometrical schemes of loading should be used and compared.
The idea that a function W(E
1
, E
2
) can be expanded into a power series, and
that it is possible to use any desirable member of series, allows one to reach a
reasonable degree of correspondence between a theoretical curve and experi
mental data, achieved by adding new arbitrary (“free”) empirical constants.
The same idea can be realized in a somewhat different way. From the very be
ginning, we can think that an elastic potential has the formof Eq 6.14, but in re
ality a material “constant” is not constant but depends on deformations. It must
be expressed as a dependence of A on invariants of the deformation tensor. It
means that nonlinearity appears not only as a consequence of large deforma
tions by itself but also as a function of some physical phenomenon (for example,
structure transformations happening in the course, and as a consequence, of
large deformations), i.e., if the simplest quasilinear potential ( Eq 6.14) is not
sufficient for fitting experimental data, then a physical nonlinear effect is en
countered.
Both approaches  expanding the dependence W(E
1
, E
2
) into a power series or
treating the material parameter A in Eq 6.14 as a function of invariants of the
deformation tensor  are a rather formal generalization of Eq 6.14. Meanwhile,
Eq 6.14 can be based on some reasonable physical arguments (“statistical theory
of rubber elasticity”) but its generalization has no such physical ground and
must be treated as an empirical relationship invented for fitting experimental
data.
The last remark in this Section relates to the time effects. Generally speaking,
time must not be mentionedinthis Chapter at all, because this concept is not con
sistent with the idea of elastic (instantaneous) reaction of a material to applied
force. This fundamental idea already has been emphasized when we said that
all stressvsdeformation relationships discussed in this Chapter are valid for
equilibrium conditions. However, there is a great difference between instanta
neous and equilibriumreactions and the gap between both is the field of time ef
fects. Moreover, large deformations and rubbery elasticity on the whole are
relevant primarily to polymeric materials and various time effects (relaxation
and all others). That is why it is very important (and insome cases very difficult)
to separate time effects and distinguish “pure” (equilibrium) stressvsdeforma
tion dependence. Nevertheless, all the above is true for equilibrium deforma
A. Ya. Malkin 207
tions. Constructing elastic potential and comparing theoretical results with
experimental data, we must be very careful in order not to go outside the bound
aries of this principle limitation.
6.5 LIMITS OF ELASTICITY
The idea of elastic behavior of a material has its natural limits. It is evident
that when stress or deformation exceeds a certain value, the material breaks. It
is opposite to the behavior of liquid, in which case the deformations (or flow)
seems to continue unlimitedly, if transitionto instability of any kind does not oc
cur. The rupture of a solidbody canalso be treatedas a limit of a steady regime of
deformations.
The stress increase eventually canleadto a macrorupture of a body andalso to
a phenomenonwhichcanbe called anelastictoplastic transition. Indeed, nu
merous experiments show that many materials behave, up to some critical
stress (or deformation), as elastic. After this critical state has been reached, the
deformations may grow unlimitedly as if a material became a liquid: this phe
nomenon is called plasticity. The situation reminds us viscoplastic behavior
discussed inChapter 5. As inthe case of viscoplastic liquids, a solid material ca
pable of elastictoplastic transition is not linear because the relationship be
tween stresses and deformations in a plastic range is not linear.
The difference between the two phenomena is rather formal but essential. We
are not monitoring what happened to a viscoplastic medium before the yield
point; in fact, the deformations are neglected up to this point and the rheological
behavior of material is only considered at stresses exceeding the yield stress. It
is quite opposite to the evaluation of behavior of plastic solids at stresses lower
than the limits of plasticity (a limiting stress analogous to the yield stress), and
deformations in this range are treated as purely elastic. Also, as a general rule,
there is not much attention given to behavior after this limit has been exceeded.
Particularly, the point of behavior change is of principle interest for evaluation
of solidlike behavior.
The critical stress (limit of plasticity or yield stress) is a characteristic point di
viding two ranges with different rheological behavior. For liquid, it is the lowest
point and measurement begins at stresses higher than this point; for solids, it is
the value of highest strain up to which a material is still elastic and thus can be
treated as a solid. Nevertheless, in both cases the method of calculation of this
state for multiaxial stress state is of primary importance and interest.
208 Elastic solids
We have already discussed the practical implications of such behavior in liq
uids. In the case of solids, the limit of plasticity determines:
• the maximal permissible load in engineering designs (because it is a mea
sure of the material strength)
• force which must be applied in different technological operations affecting
plastic deformations such as shaping of materials which proceeds by plastic
(irreversible) deformations.
It is easy to findthese limiting stresses inthe regime of uniaxial extensionor at
any other simple (unidimensional) scheme of deformation. In many real situa
tions, the superposition of different components of the stress tensor occurs at
any point. It is thus necessary to estimate some “equivalent” stress which
would lead to the critical state.
For this discussion, it is not important to distinguishwhichcritical state is con
sidered, because from a formal point of view, the rupture, yielding, or plasticity
are phenomena treated by the same terms inthe language of invariants of stress
and/or deformation tensors.
Then, the mainquestionis: whichmethod of calculationmust be followed to es
timate the equivalent stress? The answer to this question depends on the con
cept of strength discussed below. Certainly, the independent key question is:
what are the reasons for the material rupture? The discussionof physical causes
and possible mechanisms of this phenomenon is out of the scope of rheology (or
the mechanics of continuum). That is why the answer to this key question is
given in terms of stresses and deformations only, i.e., in scientific terms.
There are different possible answers to this question and they can be formu
latedas the hypothesis of strength. Among others, the four following concepts
are of primary importance. Below, we shall formulate themfor the rather simple
case when only two components of the stress tensor (normal, σ
E
, and shear, σ,
stresses) act, though it is not difficult to extend our reasoning to the complete
tensor of stresses.
α: According to a concept of maximal normal stresses, a criterion of rupture
is the exceeding of maximal principal stress. Then the criterion of strength is
1
2
[ + ( + 4 ) ] <[ ]
E E
2 2
1
2
σ σ σ σ
A. Ya. Malkin 209
where [σ] is the maximal permissible stress, or strength.
β: According to the concept of maximal deformations, the criterion of
strength for Hookean bodies is
1
2
( + ( + 4 )
1
2
( ( + 4 ) <[ ]
E E
2 2
E E
2 2
1
2
1
2
σ σ σ µ σ σ σ σ − −
]
]
]
where µ is the Poisson ratio (coefficient).
For other rheological models, this criterion certainly looks different.
γ: According to the concept of maximal shear stresses, the criterion of
strength is
σ σ σ σ
max E
2 2
= ( + 4 ) <[ ]
1
2
δ: According to the concept of maximal potential energy of deformation of a
Hookean solid, we have
( + 3 ) <[ ]
E
2 2
1
2
σ σ σ
This condition is also known as the von Mises criterion, and for simple
shear, when σ
E
= 0, it is simplified to the condition
σ
σ
=
[ ]
3
This rather simple formof the criterion is directly related to a Hookean model of
rheological behavior of a material, and for other materials the same criterion
canbe writtenina different way, adopting the idea of a critical level of stored en
ergy (at some point), but the reason for rupture remains valid.
One may see that all four concepts of strength give close, but not equivalent,
predictions concerning conditions of rupture, to some extent differing in estima
tion of relative input of normal and shear stresses into critical value of an equiv
alent limiting stress.
210 Elastic solids
6.6 SOME BASIC PROBLEMS
6.6.1 GENERAL FORMULATION
Let us discuss some fundamental problems of deformations of elastic bodies. It
is important that in some situations, stress distribution in a body can be found,
regardless of the rheological properties of a material (see Chapter 2); in other
cases, the same is true for deformations (see Chapter 3). But in the general case,
it is impossible to find (to calculate) stresses and deformations in a body if we do
not know the rheological properties of a material (i.e., the relationship between
stress and deformation “at a point”). Indeed, stress and deformation distribu
tions must be found by solving balance (equilibrium) equations with appropri
ate boundary conditions and stresses entering these equations via rheological
equations of state (constitutive equations). Therefore, the systemof equations is
not closed or incomplete, i.e., the number of variables is less than the number of
equations, if not including rheological equations of state.
One of the most important and general problems for an elastic body is formu
latedas a taskof calculating stress anddisplacement (or deformations) distribu
tions of a bar (beam) loaded at its ends by an arbitrary combination of stresses
and torques. It is called the SaintVenant problem.
The general approach to solving this and many other problems is based on the
physical idea (or supposition) known as the SaintVenant principle. Accord
ing to this concept: any statically equivalent set of forces and torques produces
the same stress distribution at distances far enough from the site of force appli
cation. This assumption excludes from consideration some areas near the ends
of a bar (beam) and states that details of force distribution (where they act) are
immaterial for solutions of balance equations almost throughout the whole vol
ume of a bar.
Certainly, the principle contains some ambiguous terms, such as “enough”and
“almost”. This uncertainty must not astonish, because the SaintVenant prob
lemand all other problems of such kind are not pure mathematical but physical
tasks, and it is necessary to find some physical arguments for their solution. One
such physical concept is a rheological equation of state which is not an inherent
part of a mathematical formulation but must be taken “from an outside”. An
other is the SaintVenant principle, which governs transition from outer forces
to the inner situation inside a material and cannot be rigorously proven. How
ever, the latter is not a very serious limitation because, as a general rule, it is
A. Ya. Malkin 211
reasonable to think that an uncer
tain distance from an end must be
of the order of a linear size of a bar
end. The longitudinal size of a bar is
much larger than its transverse
size, which means that all solutions
of the SaintVenant problem are
valid throughout the major part of a
bar, but not close to its ends. In fur
ther discussion, the solutions will
be given “excluding ends”.
The value of the SaintVenant
principle for solving the balance
equations is related to the possibil
ity to change a complex, not very
definite set of outer forces to some
simple model combinations of a
force and a torque, which must only satisfy one condition: be statically equiva
lent to the initial set.
The SaintVenant principle allows us to bring the general problemto four inde
pendent model situations (Figure 6.1):
• uniaxial extension
• bending by a pair of forces (by a torque)
• bending by a transverse force
• torsion by a torque.
The SaintVenant problem does not envelope all possible cases of loading and
deformations but contains many important situations.
6.6.2 UNIAXIAL EXTENSION (FIGURE 6.1a)
The primary analysis of the problem was given in Chapter 3. A bar (beam)
loaded by a constant force F has a uniform stress field:
σ σ σ σ
x E y z
= =
F
S
= const; = = 0
212 Elastic solids
Figure 6.1. Model cases of loading a beam (bar).
a: uniaxial extension; b: bending by a torque; c:
bending by a transverse force; d: torsion by a
twisting torque.
where x is a longitudinal direction (along an axis of a bar), y and z are transverse
directions, and S is an area of a crosssection of a bar.
If we are interested to knowdeformations, it is necessary to apply a rheological
equation of state. For example, if the Hooke Law is valid, deformations are also
uniform and are calculated as:
• in direction of stretching
ε
σ
x
E
=
E
where E is the Young modulus
• and in transverse directions for a symmetrical cross section
ε ε µε µ
σ
y z x
E
= = =
E
− −
where µ is the Poisson coefficient.
These relationships are a complete solution of the SaintVenant problem for
stretching of a bar made of a Hookean elastic material.
Hooke himself considered the possibility of nonlinear relationship between
stresses and deformations, for example, expressed by a powertype equation
σ ε
E
n
= K
where K and n are material constants.
In this case, at σ
E
= const, we have an evident solution
ε
σ
=
K
E
1
n

.
`
,
If rheological properties of material are described by the exponential function
(6.15), and σ
E
= const, then for large deformations (elongation ratio λ >>1), we
have
σ λ
E
2
= A
A. Ya. Malkin 213
and
ε λ
σ
= 1=
A
E
1
2
−

.
`
,
[6.29]
where ε is an “engineering” measure of deformations.
Now we must distinguish between two conditions: σ
E
= const and F = const.
The difference between the two cases is immaterial for infinitesimal deforma
tions because we can neglect changes of a crosssectional area in the course of
stretching, but it would not be true for large deformations. Eq 6.29 relates to the
conditionσ
E
=const, but inthe case F=const, we must use Eq 6.19, whichgives
ε λ σ = 1=
1
A
=
1
A
F
S
E
−
The last equation looks linear, as an analogue of the Hooke equation, but in
fact it is not, because the value σ
E
entering this equation is not a real stress but
some conventional measure of stress only.
Any other rheological equation of state also can be used to calculate deforma
tions. Perhaps it is worth repeating that all of them give unambiguous corre
spondence between stresses and deformations, and that time does not enter any
of these equations. It is a special case of purely elastic bodies, opposite to viscous
fluids (Chapter 5) and viscoelastic materials (Chapter 7).
Measurements of forces (and stresses) and deformations are very simple and
practical for uniaxial extension. That is why it is a basic experiment in numer
ous applications.
Two measurements are of primary importance:
• standardized testing of a material
• determining the characteristic rheological parameters of a material.
The first is of absolute importance, regardless of any particular rheological
properties of a solid. The only requirement which must be imposed is to follow
very rigorously the standard conditions of an experiment. In such a case, unam
biguous results of comparison of different materials will be obtained, useful for
quality testing of industrial products and other purposes.
214 Elastic solids
The second experimental approach is based on assumption of a type of rheolog
ical behavior of a material under testing. Comparing experimental and calcu
lated stressvsdeformation curves, a conclusion as to the correctness of the
assumptionand numerical values of material parameters entering the constitu
tive equation can be derived. It is necessary to emphasize that a negative an
swer to the question of correspondence between the experimental and
calculated results is sufficient to reject the theoretical model, but a positive an
swer is not sufficient to accept it. Various rheological models can give the same
relationships in an experiment of one type; thus experiments of different types
must be carried out to confirm or to reject a proposed rheological equation of
state.
6.6.3 BENDING BY A TORQUE (FIGURE 6.1b)
If static forces acting at the ends of a bar are equivalent to a torque, M, bending
the bar, it is possible to prove that the stress distribution is the same along the
length of a bar at all crosssections.
This balance equation for each crosssection is given by
s
E
zds = M
∫
σ
where ds is an infinitesimal area (part of crosssection), z is a distance frompoint
ds to a socalled neutral axis. Integration is done for a whole crosssection of an
area s.
Stresses are absent at a neutral axis which passes through a center of gravity
of a crosssection and is perpendicular to the plane where normal stresses act.
Only normal stresses act at this point and they counteract the bending moment,
M. No shear stresses are present, at least within the limits of small deforma
tions.
Stress distributionacross a sectionof a bar depends onthe type of rheological be
havior of a material. It is possible to showthat for a Hookean material, this dis
tribution can be represented by an equation:
σ
E
=
Mz
I
[6.30]
A. Ya. Malkin 215
The value I is given by the equation:
I = z ds
s
2
∫
Integration is carried out for the whole crosssection of a bar. I is an axial (or
equatorial) moment of inertia. It is the main geometrical characteristic of the
shape of crosssection on bending.
Eq 6.30 shows that there is a lin
ear distribution of stresses along
the height of a crosssection (see
Figure 6.2). This is true if a bar is
made of a material with rheological
properties described by the Hooke
Law.
The value I characterizes the
bending rigidity of a bar. For a
Hookean body the following rela
tionship can be proven:
1
=
M
EI ρ
whereρ is a radius of curvature of a bar (more exactly, a neutral axis of a bar). It
is evident that with I increasing, bar bending diminishes (ρ higher).
If the bar crosssection is circular (R  radius), then
I =
R
4
4
π
For a rectangular crosssection (h  height, b  width):
I =
bh
12
3
Eq 6.30 indicates that maximum stresses appear at a surface of a bar (at the
highest value of z), and that they are positive (stretching) on one side and nega
tive (compressive) on the other. This again shows that the surface is the most
vulnerable part. It may then be understood why surface reinforcement (harden
216 Elastic solids
Figure 6.2. Linear distribution of stresses along
a crosssection of a bar.
ing, chemical treatment, etc.) is frequently used in engineering practice. Also,
special profiles with increased surface (e.g., Tbeams) are used for bars sub
jected to bending forces.
If material is nonHookean, stress distribution throughout the crosssection
differs. The geometrical analysis of bending leads to a linear distribution of de
formation along a distance from a neutral axis:
ε
ρ
=
z
Only for a Hookean solid, linear stress distribution is observed:
σ ε
ρ
E
= E = E
z
After some rearrangements, the last formula gives Eq 6.30.
In all other cases, stress distribution is more complex. Bending of elastic solid
with transition to plastic deformation is one interesting example. Aplastic zone
appears at a surface. When normal stress reaches a yield threshold, this zone
moves inside the material, with an increase in torque. Stress distribution at
z ≥ z*
σ σ
E y
=
z
z*
and at z ≥ z* (closer to bar surface):
σ σ = signz
y
where z* is a distance from a neutral axis to a boarder of a plastic zone, and the
symbol sign means that the sign of a stress is determined by the sign of zcoordi
nate, i.e., stresses can be positive or negative, depending on direction from the
neutral axis.
When a plastic zone appears, a torque, M, is calculated from the equation
A. Ya. Malkin 217
M=
z*
I + S
y
e y p
σ
σ
where I
e
is a moment of inertia of an elastic core (material remains elastic), and
S
p
is a static moment of one of the plastic zones:
S = 2 b(z)zdz
p
z*
h
∫
Here h is height of a crosssection and b is width of a section (inside a plastic
zone). In the general case, b varies along z.
6.6.4 BENDING BY A TRANSVERSE FORCE (FIGURE 6.1c)
There are various modes
possible by which a trans
verse force can be applied to
a bar. However, the princi
ple concept can be under
stood fromanalysis of a sim
ple model situation when a
force is applied at the end of
a bar along the xaxis and
perpendicular to the axis of
a bar (zaxis), as shown in
Figure 6.3.
Let us consider the equilibrium state of any section of a bar at the distance, z,
from an opposite end of this bar (taken as a 0 point). Evidently, a static equilib
rium is reached when a bending moment in this section equals to
M(z) = F(L  z)
and a transverse force is constant and equal to F.
Longitudinal distributions of bending moments and transverse forces are
shown in Figure 6.4. At the crosssection of a bar on the surface of a wall, a force,
F, and a bending moment, M, have the following relationship
218 Elastic solids
Figure 6.3. A bar loaded by a transverse force at the end.
Coordinate system shown.
M = FL
Any section is subjected to the
bending torque, and a force ex
erted produces stress. The re
sultant superimposed action of
a moment, M(z), and a force, F,
at an arbitrary section of a bar
is further discussed.
In the previous Section, it was
concluded that applying torque
results in the appearance of
normal stresses across a
crosssection of a bar. Cer
tainly, normal stresses cannot
balance action of a transverse
force, F, because they are per
pendicular to each other. It
means that application of a
transverse force, F, results in
shear stresses.
Two problems thus exist which must be solved consecutively:
• it is necessary to find torque and force distribution along a bar acting at each
crosssection; this distribution is a result of action of outer forces in static
equilibrium preserved at any section of a bar;
• torques and forces at any section result in normal and shear stresses and
their calculation is based on balance equations which must be satisfied at
any local “point” of a crosssection of a bar.
The problem of calculating normal stresses as a result of torque action has
been discussed already. Now, we shall discuss the results of action of transverse
force leading to shear stress.
Distribution of shear stress in a crosssection depends on its configuration. If a
crosssection is symmetrical and the line of application of a force, F, passes
through the axis of this symmetry, then the shear stress distribution is a func
tion of the ycoordinate only and in a general case can be written as
A. Ya. Malkin 219
Figure 6.4. Longitudinal distributions of a bending
torque, M, and a transverse force, F, for a bar loaded
at its end.
σ(y) =
F
I
f(y)
x
where I
x
is a moment of inertia relative to a vertical transverse axis x (as in Fig
ure 6.3) and f(y) is a function of a vertical coordinate y only.
For example, if a crosssection is rectangular, and its vertical size is H, the hor
izontal size is b, then σ(y) is expressed as follows:
σ(y) =
3F
2bh
1
2y
H
2
−

.
`
,
]
]
]
]
where y = 0 is a horizontal axis of a rectangle.
Then maximal shear stress σ
max
acts at an axis and it is
σ
max
=
3F
2bH
If a crosssection is a circle with a radius, R, the maximal shear stress acts at
the horizontal axis and it is
σ
π
max
2
=
4F
3 R
The theory of bending by a transverse force gives three main results:
• stress distribution at any crosssection of a bar, offering concept of strength
and rupture of a material;
• deformation of a material at any point;
• deflection (macrodeformation or macrodisplacement) of a bar.
There are two distributions at any crosssection of a bar (beam) bent by a
transverse force:
• distribution of normal stresses σ
E
(y)
• distribution of shear stresses σ(y).
One canfindσ
E
andσ for any point of a crosssection. Therefore, it is important
to calculate principle stresses as a functionof σ
E
andσ. According to the theoret
ical results included in Chapter 2, it is easy to show that
220 Elastic solids
σ σ σ σ σ
1,2 E E
2 2
3
=
1
2
[ ( + 4 ) ]; = 0
1
2
t [6.31]
Inorder to calculate deformations at any point, it is necessary to use a rheologi
cal equation of state. In the simplest case, it is the Hooke Law, and the resulting
formulas can be easily found in numerous textbooks on strength of materials.
Deflectionof a bar depends onits rigidity. The latter termis evident, ona quali
tative level, and as a quantitative termrigidity of a Hookean body is determined
by a product EI
x
, where I
x
is the moment of inertia of a crosssection of a bar.
Deflection of a bar loaded by a transverse force varies along the length of a bar.
It is quite evident that maximal deflection, f
max
, for a force applied at the end of a
bar (as shown in Figure 6.3) takes place at this end. Its absolute value is
f =
FL
3EI
max
3
x
where L is a length of a bar.
The mode of loading shown in Figure 6.3 is only one of possible cases of the ap
plication of a transverse forces. Certainly, the number of possible schemes of
loading is unlimited, and eachof themmodels real situations met inengineering
practice. Theory of strength of materials gives methods used for calculation of
bending torques and transverse forces at any crosssection of a bar. These meth
ods are based on general balance equations of a bar, which were illustrated by
the abovediscussed example of transverse force applied at the end of a bar.
Another interesting example is given below to demonstrate the differences in
results for two cases. This is a loading
of a bar by a transverse force applied at
the central plane with a position of
both ends of a bar fixed in space, allow
ing bar to turn, as shown in Figure 6.5.
This mode of loading is typical in many
applications, and in particular, this
scheme is used for testing materials
according to standards.
A. Ya. Malkin 221
Figure 6.5. A bar loaded by a transverse
force applied at the center.
A bending torque (moment) and a trans
verse force distribution for this mode of
loading are drawn in Figure 6.6.
Let us discuss characteristic parameters
for a bar of the length, L. Some of themare
quite evident from the balance equations.
That is:
• forces acting at the ends of a bar F
o
and
F
L
(resistance of supports) are equal to
F = F =
F
2
o L
• torque (bending moment) at the cen
tral plane of a bar whichis the maximal
torque M
max
is
M =
FL
4
max
The central plane is the most “vulnerable” crosssection because a bending
torque and a transverse force are maximal here. Based on these values of a mo
ment and a force, one can find stresses for any shape of a crosssection (as was
done above) and estimate the strength of a bar according to the accepted concept
of rupture.
The other useful parameter needed in engineering practice is the maximal de
flection, f
max
. Certainly, it occurs in a central plane and is equal to
f =
FL
48EI
max
3
x
More examples can be found in other textbooks and/or reference books. It
should be remembered fromthis discussion that the majority of formulas avail
able in these books are valid for Hookean materials.
222 Elastic solids
Figure 6.6. Distributions of a trans
verse force and a bending torque along
a bar loaded at the central plane.
Our next discussion is devoted to the cases of some of the simplest deviations
fromHookean behavior. The first illustration is the situation when properties of
a material are different in compression and extension. In bending, the different
layers of a bar are either compressed or stretched.
For example, in application of a force as in Figure 6.5, lower layers of a bar are
stretched and upper ones are compressed. It does not influence the result of ap
plied calculations if a material is Hookean. But even in the case when behavior
of a material is still Hookean but moduli in extension, E
T
, and compression, E
C
,
are different, the results of calculations differ as well. In fact, it can be proven
that all formulas obtained for a Hookean material can be used but the Hooke
modulus of elasticity must be substituted by an apparent modulus, E
a
, which is
calculated via moduli in extension, E
T
, and compression, E
C
, as
E = E
2(E E )
(1+ (E E )
a T
T C
T C
2
1
2
1
2

.
`
,
[6.32]
The Eq 6.32 can be used to determine the modulus of elasticity in compression.
For this purpose, the modulus in extension, in a standard experiment of speci
men stretching, must be determined and then an apparent modulus in bending
must be measured according to the schemes inFigures 6.3 or 6.5. As a result, the
modulus of compression can be calculated from Eq 6.32.
The next illustration of nonHookean behavior in bending by transverse force
is related to the case when rheological properties of a solid (elastic) material are
described by a power law:
σ ε
E
n
= A
where A and n are material parameters of a nonHookean body.
Let a crosssection of a bar be a rectangle of the height, H, and width, B. We
shall discuss the mode of loading showninFigure 6.5. The moment of inertia of a
crosssection, I
x
, is BH
3
/12. If rheological properties of a material are Hookean,
then according to the above formulas, its flexure in a central plane is
A. Ya. Malkin 223
f =
FL
4EBH
max
3
3
If rheological properties are described by a power law, the expression for a maxi
mal flexure becomes
f =
n
n+ 1
L
2H
n+ 2
2
FL
ABH
max
3
2
1
n
]
]
]
It is evident that for n = 1, the latter equation transforms to the equation for
flexure of a Hookean body. It is essential to note that the moment of inertia of a
crosssection does not appear in the latter equation in a clear form, meaning that
the theory of stresses and deformations for any nonHookean material must be
redesigned when a rheological equation of state (constitutive equation) is cho
sen.
Let us nowdiscuss such a rheological effect as plasticity in relation to bending.
InSection6.5, it was emphasizedthat there are some natural limits of elastic be
havior of solids. One of themis determined by plasticity of materials. According
to this rheological model, a material can be treated as an elastic (Hookean) up to
the yield stress σ
y
, and at σ
E
= σ
y
, yielding takes place.
Plastic behavior of solids results fromspreading of a plastic zone fromthe point
at whichthe stress state attains a critical point corresponding to the yieldstress.
According to the theory of bending of a Hookean body, the most vulnerable
point is positioned at the surface of a bar. If a crosssectionis a rectangle, yielding
occurs when a torque is
M =
BH
6
y
2
y
σ
It is possible to increase the bending moment, but suchactiondoes not result in
increase of stress because it cannot exceed the yield stress. It means that by in
creasing the torque, a plastic zone is widened. Then, if M> M
y
, transverse stress
distribution is as shown in Figure 6.7. In this case, the plastic zone corresponds
to a part of a crosssection in which σ
E
= σ
y
= const.
224 Elastic solids
Plastic behavior inbending leads to the ef
fect of plastic collapse in flexure, which is
evident from the dependence of deflection,
d, at the central plane of a bar on the ap
plied load, F, as in Figure 6.5. When a plas
tic zone appears and then begins to spread
throughout a crosssection, the deflection
increases with a higher rate than a trans
verse force because the resistance (rigidity)
of a material also decreases. This effect is il
lustrated inFigure 6.8. The initial slope of a
straight line is equal to (L
3
/4EBH
2
) since it
is within a Hookean limit. Then, at the
point A, a plastic zone appears and anaccel
eration of the deflection growth is observed.
Finally, at some critical force, F
y
, calculated
as
F =
BH
L
y
2
y
σ
the deflection increases limitlessly without
a further increase in force because at this
point a plastic zone occupies the whole
crosssection. This unlimited growth of the
deflection can be called plastic collapse.
It is also interesting to mentionthat inthe
range of forces between F
A
and F
y
, a plastic
zone is spreading not only into the center of
a bar throughout the crosssection but also
fromthe central plane to the endsupports.
In the previous discussion, it was as
sumed that a line of application of a trans
verse force passes through the center of a
crosssection. In reality, it is not always the
case, as shown in Figure 6.9. A line of force
A. Ya. Malkin 225
Figure 6. 7. Stress distribution
througha crosssectionof a plastic ma
terial when yielding begins.
Figure 6.8. Dependence of deflection,
ina centrally loaded beam, ona load if
stresses pass throughthe yieldpoint.
action can pass through the center
of a crosssection. According to the
fundamental SaintVenent princi
ple, this situation can be substi
tutedby a statically equivalent sum
of a transverse forces passing
through the center and a twisting
moment (torque) as drawn in Fig
ure 6.9. It shows that byforce can
be represented as a combination of
bending (discussed above) and tor
sion(discussedinthe next Section).
6.6.5 TORSION OF A BAR (FIGURE 6.1d)
Torsion or twisting of bars (beams) is a very popular model of numerous cases
of applied engineering practice. Indeed, shafts, power transmissions, twisting
springs, screws, and many other devices are subjected to twisting torques, fre
quently causing deformation and even breakdown of these components. It is
thus important to have a method for calculating stresses acting in a bar and its
deformations.
The formulation of the problem consists of the application of a twisting torque
(moment), M
z
, (around the zaxis) at an end of a bar. Then, it is possible to show
that only shear stresses σ
xz
and σ
yz
are nonzero and that they do not depend on
the zcoordinate, i.e., the distribution of stresses is constant along the axis of a
bar, though stresses depend on transverse coordinates. It is necessary to find
stresses and deformations in a bar. Besides stresses and deformations “at a
point”, it is also important to estimate the relative angle of turn, φ
sp
, of a
crosssections along the length of a bar. This value is defined as an angle of a rel
ative turn of two crosssections, separated from each other by distance, L.
Ageneral solution to the problemunder discussion is rather complex, but sim
ple and quite evident results for ordinary shapes of a crosssection can also be
obtained. For a circular crosssection, the distribution of shear stresses along
the radius σ(r) is
226 Elastic solids
Figure 6.9. Bending by a transverse force pass
ing the center of a crosssection.
σ =
M
I
r
z
p
[6.33]
where I
p
is a polar moment of inertia of a crosssection, defined for an arbitrary
geometrical form of a crosssection as
I = r ds
p
2
s
∫
Then for a round crosssection, I
p
is
I =
R
2
p
4
π
and for a cylindrical crosssection
I =
R
2
(1 )
p
4
4
π
β −
where Ris anouter radius of a cylinder, andβis the ratio of inner to outer radii of
a cylinder.
The maximal shear stress σ
max
is
σ
π
β
max
z
3
4
=
2M
R
(1 ) − [6.34]
For a thinwalled cylinder when β << 1, shear stress can be considered as con
stant through the wall, and calculated as
σ
π δ δ
=
2M
(2R+ )
z
2
where R is a radius of a cylinder and δ is the width of a wall (δ << R).
For a round crosssection β = 0 and σ
max
can be found as
A. Ya. Malkin 227
σ
π
max
z
3
=
2M
R
Torsion of a straight bar causes a turn of neighboring crosssections along the
length of a bar relative to each other. The angle of a turn, φ, depends on rheologi
cal properties of a material. For a Hookean body
φ(z) =
M
GI
z
z
p
[6.35]
i.e., φ is a linear function of a longitudinal coordinate z.
If a net length of a bar is L, the angle of a turn between ends of a bar φ
max
is
φ
max
z
p
=
M L
GI
where G is shear modulus of a Hookean body.
The relative angle of turn can be found as
φ
sp
z
p
=
M
GI
and the maximal stress can be correlated with the relative angle of turn
σ
max sp
= GRφ [6.36]
The value of the product GI
p
can be called rigidity in torsion, and the higher
this product is, the lower the value of turn along the length of a bar.
In the engineering practice of design of shafts, transmitting power, etc., the ac
ceptable limit for the twisting torque can be chosen, either based on maximal
stress (if strength is a limiting factor) or a number of permissible turns calcu
latedas anangle of twisting per anunit of length(if rigidity is a limiting factor).
228 Elastic solids
In twisting of round bars, when deformations are
small, all crosssections remain parallel to each
other. In other shapes of crosssections, even for
such simple ones as square or elliptic, the
deplanation effect takes place, even in the limit of
infinitesimal deformations, i.e., distortion of plane
sections is necessary to maintain a continuity of
deformations.
In engineering practice, it is common to observe
defects on the surface of a shaft. Such local defects
are especially important for torsioneffects because
shear stresses are maximal at the surface. Atypical example is shown in Figure
6.10, where a small semiround hole of a radius, R
h
, is made on the surface of a
bar (shaft). In this case, the maximal shear stress is
τ
max
p
h
sp
h
=
2MR
I
1
R
2R
= 2GR 1
R
2R
−

.
`
,
φ −

.
`
,
and comparing this formula withEq 6.36, one cansee that a small surface defect
results in doubling shear stresses.
Crosssections other than circular can also be met in engineering practice. In
many cases, the analytical solutions to boundary problems are also known,
though they can be formulated to series or approximate formulas. For example,
for a shaft of a rectangular crosssection(His its height, and Bis its width), maxi
mal shear stress can be calculated as
σ
π π
max sp
2
GB 1
8 1
cos
H
2B
≈ φ −

.
`
,
]
]
]
]
]
]
[6.37]
However, discussing deformations in twisting of nonround bars, we must not
forget about the effect of deplanation, whichalways appears inall these cases.
In the case of torsion of thinwalled cylindrical shafts, it is easy to followthe ef
A. Ya. Malkin 229
Figure 6.10. Crosssection of
a round shaft with surface
defect.
fect of plasticity in relation to the yield stress in shear, σ
y
, because stresses are
almost uniform throughout the crosssection. If we accept that yielding in shear
deformations takes place according to the von Mises condition, then
σ σ = 3
y
we can find that the torque value, M
y
, causing yielding is
M =
2 3
(2R+ )
y y
2
π
σ δ δ
In the case of a nonuniform stress field, the critical condition is reached at a
certain point but not throughout the whole crosssection simultaneously.
6.6.6 TEMPERATURE STRESSES
Change in temperature results in expansion (or compression) of a material. If
deformations of such kind are prevented by outer boundaries, internal stresses
appear ina body. This effect is well knownand must be takeninto account innu
merous applications. For example, it is important to maintain gaps between
neighboring rail sections because the temperature change would otherwise dis
tort them.
In the simplest model of temperature
stresses, we can consider a bar between two
rigid (nondeformed) walls (Figure 6.11). In
fact, it is model of an abovementioned situa
tionof a rail sectionplaced betweentwo others.
Let temperature of a bar increase by T, assum
ing that walls prevent free movement of the
bar. It means that the normal stresses appear
in a material and their value can be calculated
as
σ α
E
= E T ∆ [6.38]
whereα is a coefficient of linear thermal expansion, andEis the Young modulus,
as usual.
230 Elastic solids
Figure 6.11. Abar placedbetween
two rigid walls: stresses appear
ing due to temperature increase.
Temperature stresses exist not only in bodies restricted by outer boundaries
but in materials which may have unrestricted movement but the temperature
field inside them is not homogeneous. In this situation, stresses at boundaries
are absent but they exist inside a body and their value depends on temperature
distribution.
6.6.7 CYLINDER UNDER INTERNAL PRESSURE
We shall consider stresses and deformations in walls of a thinwalled cylinder
with an internal pressure, P. This scheme is a quite evident model of many real
situations, for example, tanks working under pressure.
A definition of a thinwalled cylinder is
δ << R
where δ is the width of a wall, and R is an inner radius of a cylinder.
The primary discussion concerning components of the stress tensor in a
thinwalled cylinder has been already included in Chapter 2. Here, some addi
tional “rheological” arguments are introduced to this discussion.
α For a Hookean body (in the limits of small deformations), it is easy to find de
formations. According to the definition of the Hookean body, it is evident that
ε σ µσ
θ θ
=
1
E
( )
z
−
where ε
θ
is a circumferential component of the deformation tensor, and σ
θ
and
σ
z
are components of the stress tensor.
Components of the stress tensor for different modes of loading of a cylinder
(open or closed ends) were calculated in Chapter 2. Now, we can find deforma
tions.
β Let an elastic material become plastic at some value of yield stress, σ
y
. There
are two components of the stress tensor σ
θ
and σ
z
acting in a wall. According to
the von Mises criterion, the relationship between the yield stress and compo
nents of the stress tensor is as follows,
A. Ya. Malkin 231
σ σ σ σ σ
θ θ y
2
z
2
z
= ( + )
1
2
−
If ends of a cylinder are open, σ
z
= 0, and
σ σ
θ
=
z
If a cylinder is sealed (ends are closed)
σ σ
θ
=
2
3
y
From the above equations, one can find critical (limiting) pressure correspond
ing to a transition of a material into a “plastic state”.
γ Let us discuss the situation when rheological properties of a solid body are
described by the MooneyRivlin potential function which is formulated via the
first and second invariants of the tensor of large deformations
W =
A
2
(I 3) +
B
2
(I 3)
1 2
− −
where A and B are material constants.
If one assumes that a material is incompressible, then it is possible to show
that the stress components are
σ λ λ
λ λ
θ θ
θ
= (A + B )
1
z
2 2
2
z
2
−

.
`
,
and
σ λ λ
λ λ
θ
θ
z
2
z
2
2
z
2
= (A + B )
1
−

.
`
,
where λ
θ
and λ
z
are principle ratios of extension in two directions.
232 Elastic solids
The general solution for λ
θ
and λ
z
can be found from these equations without
problems. It is simpler to illustrate the solutionfor the case whenB=0, the more
so when B << A, and it is reasonable to neglect B in comparison with A. For this
case
λ
λ
λ
θ
θ
z
2
· + +

.
`
,
]
]
]
]
2
6
1 2
4
1 1
8
/
Now, we canexcludeλ
z
inequations for stress components, andfindσ
θ
andσ
z
in
an analytical form. Perhaps the final expression looks cumbersome, but it is
quite possible to use it to calculate deformations of, for example, an elastic cylin
der made of a rubbery material under an internal pressure.
6.6.8 PRESSURE INSIDE A SPHERE
Let us attempt to calculate stresses and deformations in the wall of a sphere
loaded by internal pressure, p. It is evident that due to the central symmetry of
the body, all shear components of the stress tensor are equal zero, and normal
stresses (which are the principle stresses) must be found in a polar (spherical)
coordinate system. Two of themare equal (σ σ
θ
=
φ
), and we need to calculate ra
dial normal stress σ
r
, where θ, φ, and r are spherical coordinates.
If an inner radius of a sphere is R
i
and outer radius is R
o
we have the following
boundary conditions
at r = R
i
σ
r
= p;
at r = R
o
σ
r
= 0.
where r is a current radius (R r R
i o
≤ ≤ ).
The solution for a Hookean medium is well known and is expressed as
σ σ
r av
o
3
= = 1
R
r
−

.
`
,
]
]
]
]
σ σ σ
θ
= = 1 +
1
2
R
r
av
o
3
φ

.
`
,
]
]
]
]
where an “average” stress σ
av
is
A. Ya. Malkin 233
σ
av
i
o
3
i
o
3
= p
R
R
1
R
R

.
`
,
−

.
`
,
Deformations and displacements can be easily calculated according to the defi
nition of a Hookean body.
Now, it is interesting to investigate the critical conditions for elastictoplastic
transition. If we assume that this transition occurs due to the action of shear
stresses and is described by von Mises criterion, then maximal shear stress σ
max
acts at the inner surface of a sphere and can be calculated as
σ σ
max av
o
i
3
=
3
2
R
R

.
`
,
The critical value of pressure p* inside a sphere, which corresponds to elas
tictoplastic transition, can be found from equation
p *=
2
3
R
R
R
R
1
o
i
3
o
i
3
y

.
`
,

.
`
,
−
]
]
]
]
σ
where σ
y
is the normal stress at which elasticto plastic transition (or yielding)
takes place in uniaxial extension.
The last equation allows one to calculate the limiting pressure in thin balloons
made of plastic materials or to find permissible pressure in highpressure chem
ical reactors.
6.6.9 STRESSES AND DEFORMATIONS IN MEMBRANES
Membranes loadedby forces normal to their surfaces are a standardelement of
many engineering designs. In all these cases, a membrane can be regarded as a
thinsheet whichdoes not resist shearing, and therefore, bending moments at all
points of a membrane are absent. Aloadedmembrane is a goodapproximationof
234 Elastic solids
shells, thin sheets, films, and so on.
In the limit of infinitesimal (or small enough) deformations, the shape of a
membrane does not change under loading. Static equilibrium and forces and
then stresses can be calculated from appropriate balance equations.
A typical example of a loaded membrane is a hemispheric cup under its own
weight. The stress analysis of this problemwas conducted in Chapter 2. If defor
mations are small, they can be easily calculated fromthe stress distribution ac
cording to the Hooke Law. In this case, rheological arguments practically do not
add anything new to the stress analysis, except for deformations and relative
displacement points of a membrane, and since they are small, they do not result
in distortion of a shape of a membrane.
The situation becomes more complex if large (final)
deformations occur, and one must consider large dis
placements and distortions of the shape of a mem
brane. As an example, let us follow deformations in a
flat membrane which budges due to the action of ex
ternal forces (Figure 6.12). This is a typical case of
large deformations and it is rather instructive to fol
low complications which appear in the analysis of
this problemdue to large deformations and distortion
of a shape of a membrane.
First of all, we do not know the final shape of a membrane which is definitely
different than its initial shape. In the case under discussion, it is reasonable to
think that an initially flat sheet becomes closer to a sphere. Then, its shape can
be approximated by a formula
r = Rsinα
where R is a radius of a membrane and α is an angle calculated from an axis of
symmetry.
Balance equations showthat specific (i.e., calculated per unit of the length of a
membrane) circumferential force, F, and meridional force, F
θ
, are the same and
both can be found as
F = F =
Pr
2sin
=
PR
2
l θ
α
A. Ya. Malkin 235
Figure 6.12. Budging of
a flat membrane due to
where P is pressure required to bulge a membrane.
As a result of this equality, both components of principle extension ratios must
also be equal:
λ λ
θ
=
1
Both extension ratios can be easily found from purely geometrical arguments
and they are
λ λ
θ
= =
R+ (R r )
R+ (R a )
1
2 2
2 2
1
2
1
2
−
−
where 2a is the initial size of a membrane.
Extension ratios can also be expressed via central (maximal) deflection,
f, which is related to R by an equation
R =
a + f
2f
2 2
Substituting, we obtain
λ λ
θ
= =1 +
fh
a
1
2
It is interesting to calculate the thirdprinciple extensionratio, λ
r
. Fromthe as
sumption of the constant volume of a material in deformations, the value of λ
r
is
calculated from equation
λ
λ λ
θ
r
1
2
2
=
1
=
1
1 +
fh
a

.
`
,
The last equation shows that the reduction of membrane thickness is not uni
form. It does not occur near the ends of a membrane (where h = 0 andλ ·1) and it
236 Elastic solids
the largest at the top, where h = f and
λ
r,max
2 2
=[1+ (f a) ]
Infurther analysis, it is confirmed that the assumptionabout spherical formof
a deformed sheet is rather artificial, and as a result, one may come to the conclu
sion that deformations are absent at the ends of a membrane, meaning that
stresses must be zero at the edge. Certainly, this is not the actual case and such
a solution is invalid near the edge. That is why it is reasonable to use an aver
aged value of λ
r
, determined as
λ
r,av
0
f
2
2
=
1
f
1+
fh
a
dh
∫

.
`
,
and
λ
r,av
2
\1
= 1+
f
a

.
`
,
]
]
]
]
Two other averaged values of extension ratios are
λ λ
θ,av i,av
2
= = 1 +
f
a
1
2

.
`
,
]
]
]
]
We can use any stressvsdeformation relationship to calculate λ
i, av
for known
stresses in a membrane. They are
σ
δ
1
o
2
=
PR
2
1 +
f
a
1
2

.
`
,

.
`
,
]
]
]
]
where δ
o
is the initial thickness of a membrane and its final thickness δ is ex
pressed as
A. Ya. Malkin 237
δ
δ
=
1 +
f
a
o
2

.
`
,
For example, let a nonlinear relationship between stresses, σ, and deforma
tion, ε, be expressed by an elastic potential (6.14). Then
σ σ λ
λ
θ l 2
4
= = A
1
−

.
`
,
where
λ λ λ
θ
≡
lN
=
For the purpose of further simplification, we canassume thatλ >>1, andthen
σ λ
E
2
= A
Now, it is possible to showthat the resulting formula has the following form:
Pa
2
= A
2
f
a
1 +
f
a
o
2
δ

.
`
,

.
`
,
The last equation allows us to calculate the
deflection, f, as a solution of the quadratic
equation and to find dimensions of a de
formed membrane.
6.6.10 CONTACT (LOCAL) STRESSES
Let us assume that a force, F, is acting nor
mal to the surface of an elastic body at “a
point”. Formally, it means that the intensity
(specific force, or force divided by an area on
which it acts) of the local force at this point is
infinite. Inreality, any force, evenvery local
238 Elastic solids
Figure 6.13. A local force acting at a
solid elastic surface. Plastic (A) and
elastic (B) zones around the top of a
wedge penetrating into a solid mate
rial.
ized, acts onsome finite area andstresses cannot be infinite. Moreover, any force
results in deformations of a material and reorganizes an area where it is ap
plied. The stresses created are called contact stresses, and they are discussed
below. Now, we shall consider the case of “point” application of a force (Figure
6.13).
Thougha force cannot be applied to “a point”, this scheme is a good model of nu
merous real situations; for example, nails driven into a solid wall, a heavy wheel
on a road, a ball in a ball bearing, etc.
Solution of the problem under discussion can be easily formulated in polar co
ordinates, which are introduced as
x= r cos ; y = r sin θ θ
where r is the distance fromthe point of force applicationandθ is a polar angle.
Then, it is possible to find that for a Hookean elastic material, absolute values
of the components of the stress tensor are
σ
π
θ
θ
xx
2
=
2F sin
r
cos
σ
π
θ
θ
yy
2
=
2F sin
r
sin
σ
π
θ
θ
xy
2
=
F sin
r
sin
It is also possible to find principal stresses
σ σ
π
θ
1 2
= 0; =
2F sin
r
Certainly, all these equations are invalid in the close vicinity of the point of
force application because the true force distribution around this point is not
properly modeled. Nevertheless, the results of calculations are rather interest
ing because they showthat stresses are decreasing rather slowly fromthe point
of force application, proportional to the distance from this point.
A. Ya. Malkin 239
If a material becomes plastic, which happens with stresses exceeding the yield
stress (whenσ σ >
y
), we arrive at a rather interesting picture drawn in a quali
tative formin Figure 6.13. Near the top of a wedge penetrating into a solid body,
a plastic zone appears, surrounded by an elastically deformed material. This
scheme of deformation reflects a situation common to many technological pro
cesses of the shaping of solid (elastic) materials which become capable to plastic
deformations at σ σ >
y
(i.e., they conserve a newformcreated by an action of ex
ternal forces if they exceed the yield stress). Certainly, the form of material de
formation can vary, but a zone of plastic deformation appears near the sharp
edges of material breakdown; for example, near the corners of a rectangular
punch. If the rheological equation of state (constitutive equation) of such elastic
material, transiting into a plastic state at σ σ >
y
, is known, then it is possible to
calculate stress and deformation distributions through the volume of a body.
Calculation of contact stresses in solid bodies under force, F, deserves some ex
planation. It is socalled Hertz problem, and its solution depends on the shape
of the body whichexerts this force. If bothmaterials are Hookeanand their rheo
logical properties are characterized by the same value of the Young modulus, E,
the equations, for the maincases, are well known. For example, if two contacting
bodies are spherical, the maximal stress, σ
max
, is calculated as
σ
max
2
1 2
2
1 2
2
= 0.388 FE
(R + R )
(R R )
1
3
]
]
]
where R
1
and R
2
are radii of contacting spheres.
If one of the spheres is replacedby a flat plane (i.e. if R
1
=0 andR→ ∞), we have
σ
max
2
2
= 0.388
FE
R
1
3

.
`
,
It is interesting to mentionthat inall cases whentwo Hookeanbodies are incon
tact, and one of themis a sphere, the maximal stress is proportional to the com
plex (FE
2
)
1/3
. As a general rule, an elastic material can sustain great contact
stresses. It is explained that a contact force leads to a threedimensional com
pressive stress state, which is not as dangerous to a material as tensile stresses.
240 Elastic solids
It is possible to prove that the most dangerous point is positioned not on the sur
face at the place of a contact but at some distance under the point of contact, and
the principle stresses in this point are lower than the maximal stress, σ
max
. That
is why plastic deformations with the yield stress exceeded occur inside the vol
ume of contacting bodies before they can spread to the surface.
6.7 CONCLUDING REMARKS
Agreat number of materials used in engineering practice and in numerous ap
plications can be treated as solids or elastic solids. It means that the energy of
deformationis storedinamaterial, andafter the actionof external forces ceases,
this stored energy is used for restoration of the initial form of a body. In this
sense, we may say that anelastic material remembers the history of its deforma
tion. Anideal elastic material stores and returns the energy of deformationcom
pletely and instantaneously. It is interesting to mention that the work of
deformation of an ideal elastic material does not depend on the route from the
initial to the final configuration. That is why stored energy is a potential func
tion (i.e., a function which does not depend on the manner of movement in space
of variables but depends on positions of starting and final points in this space
only).
Certainly the concept of ideal elasticity is only a model of behavior of real solid
materials in which elastic (recoverable) deformations dominate. In reality, nei
ther is storage of energy of deformation complete (part of it dissipates even
though it can be only a slight part of the full energy involved) nor is the reaction
of a material after removal of external loading instantaneous (though it can be
very rapid). Moreover, the same material can behave differently, depending on
the timescale of deformations. An idea of elasticity is primarily related to the
behavior of a material, rather than to the material itself, though this difference
does not appear obligatory and in some cases can be evaluated in speciallyde
signed experiments (in a very prolonged observation only).
Moreover, even if a material is elastic (or close to the ideal elastic behavior),
this type of rheological property can exist up to a definite limit of stresses. This
limit is restricted by one of the two reasons:
• rupture of a material when stresses exceed its strength
• transition to a plastic state if stresses exceed the yield stress of a material.
Both critical situations are predicted on the basis of a concept of an “equiva
lent” state calculated as a function of invariants of stress and/or deformation
A. Ya. Malkin 241
tensors. This formal approach does not answer the question regarding the rea
sons for rupture or elastictoplastic transition, and generally the answer is out
of sphere of rheology, belonging rather to the physics of solid state. This is not
surprising because the reason for material to obey the Hooke Law is not dis
cussed in mechanics (or rheology of continuum) since it belongs to the physics of
solids. According to the classification of the rheological effects (Chapter 3), we
only can state that both phenomena can be treated as manifestations of phase
nonlinearity in the rheological behavior of a solid material. It is rather evident
from transition to plastic state, for example, in neck formation on uniaxial
stretching, but the same can be valid in relation to rupture.
The existence of the limiting point for elastic materials is outside of the concept
of elasticity and must be introduced from some independent arguments. This
point is very important for all applications, because a model of an elastic mate
rial is very widely used for countless engineering problems and it is necessary to
know the limits of its applicability.
The central position in rheology of solids is occupied by the search for a valid
rheological equation of state (constitutive equation) used for description of me
chanical behavior of real material. There are two rational ways to build a rheo
logical equation of state for an elastic material. The first is based on the
fundamental concept of elasticity and representation of an elastic energy of de
formations (or elastic potential function) in the formof a combination of stresses
and deformations. The second approach utilizes possible versions of reasonable
relationships between stresses and deformations. Both methods formulate rhe
ological equations of state ininvariant form, i.e., they are basedonrational func
tions and may relate invariants (or principal values) of the stress and
deformation tensors. It is always possible to switch from one method of formu
lating to the other.
The simplest rheological equation of state of an isotropic elastic body is the
Hooke Law, which postulates the linear relationship between normal stresses
and deformations in uniaxial extension and introduces two rheological (mate
rial) parameters
• the Young modulus, which is determined as a coefficient of proportionality
between stresses and deformations in uniaxial extension. The value recipro
cal to the Young modulus is called elastic compliance (in extension)
• Poisson ratio, which is an absolute value of the ratio of transverse to longi
tudinal deformations measured in uniaxial extension.
242 Elastic solids
Generalization of the Hooke equation to threedimensional deformations can
not be done in a straightforward way, because the simplest possible assumption
that all components of stress and deformation tensors are proportional to each
other is evidently wrong. Such generalization requires splitting of both tensors
into spherical and deviatoric parts, and only for these components of tensors
separately does the idea of linear proportionality work well and allow one to
build a reasonable rheological equation of state of the simplest elastic body
whichis correct for the range of small (or infinitesimal) deformations. This is the
simplest possible model which includes two independent material parameters
(coefficients of proportionality) of a medium called the Lamé factors. Their
physical meanings are:
• modulus of volume compressibility, characterizing the resistance of a
material to homogeneous volume changes, under hydrostatic pressure,
without changes in shape of a body;
• shear modulus, characterizes resistance to changes inthe formof a body at
its constant volume.
Any pair of constants can be recalculated to each other so there are only two in
dependent constants which represent rheological properties of an isotropic elas
tic material. Moreover, a medium is incompressible when Poisson ratio is 0.5
and only one independent constant describes mechanical behavior of an isotro
pic elastic material. It can be the Young modulus or shear modulus.
If an elastic material is anisotropic, i.e., its properties depend on directions of
force application and deformation measurements, the number of independent
constants (moduli or compliances) is more than 2 and their exact quantity de
pends onthe class of symmetry of ananisotropic material. For example, it is true
for monocrystals, liquid crystals, reinforced plastics. The maximal number of in
dependent constants for bodies of the highest class of symmetry is 21 and this
number diminishes with a decrease in the class of symmetry.
Elastic deformations can be large (in comparison with 1), and in this case, it is
necessary to refer to the theory of finite deformations in order to construct a rhe
ological equation of state.
Ageneral approachto solving this problemconsists of anapplicationof various
hypotheses concerning functional dependencies of anelastic potential oninvari
ant of the tensor of large deformations. The simplest case is an assumption of
linear dependence of an elastic potential on the first invariant of this tensor or
on the combination of the first and the second invariants, and so on. If it is not
A. Ya. Malkin 243
sufficient, it appears necessary to introduce higher members of the series with
own coefficients (material constants). The same results are achieved if we use
linear combinations of the CauchyGreen and Finger tensors of large deforma
tions.
In all these cases (even if we use linear members of the series only), the
stressvsdeformation relationships in extension become nonlinear, though
they may stay linear for shear deformations. It demonstrates that the same re
sults obtained in an experiment of one type can be compatible with qualitatively
different results of an experiment in another geometrical scheme of sample
loading. It is thus necessary to combine different geometrical modes of loading if
a solid conclusionabout the type of the rheological equationof state of a material
is expected.
Rheological equations of state of an elastic solids are used to solve boundary
problems, i.e., they are used to find stresses and deformations inside a body
loaded on its surface, and sometimes macrodeformations (for example, deflec
tions and twisting of bars) are also a subject of investigation. There are different
classes of boundary problems. Among them, the SaintVenant problemis one
of the most popular and important. This problem is formulated as a task of cal
culating stresses and deformations inbars (beams) loaded at their ends inanar
bitrary manner, primarily by a stretching force, by a transverse force, by a
bending torque (moment), or by a twisting torque.
The general approach to solving this problem is based on the SaintVenant
principle. According to this concept, the resulting distribution of stresses in
side a material does not depend on detailed manner of force and torque applica
tion at the ends of a beam, if direct vicinity of the ends is not of special interest.
This approach allows one to find normal and shear stresses (and then principle
stresses at any point) at any crosssection of a bar of an arbitrary form. These so
lutions are very widely used in engineering practice for calculating strength of
materials. When stresses exceed the yield stress, plastic deformations appear in
the the center of action of maximal stresses, and plastic zones are spreading
throughout a sample.
Besides the SaintVenant problem, other situations also can be investigated, if
the rheological equation of state of a material is known. The contact stresses in
case a highly localized force applied to the surface of a body canbe other example
of application. As a result, the stress distribution through the volume of a body
canbe foundandthe transitionto plastic deformationat yieldstress estimated.
244 Elastic solids
7
VISCOELASTICITY
7.1 INTRODUCTION
Rheological behavior relatedto viscoelasticityis the most relevant for the de
scription of a majority of real materials. Viscoelastic effects exist in Newtonian
liquids (e.g., water) under special conditions of measurement, such as very high
frequencies. The other extreme of viscoelastic effects is offered by the example of
vibration damping in bells, due to “viscous” losses in metal.
In general, viscoelasticity is a combination (or superposition) of properties
characteristic for liquids (viscous dissipative losses) and solids (storage of elas
tic energy). Therefore, a general definition of viscoelastic materials includes two
components — elastic potential and intensity of dissipative losses. However,
these two values are factors of a different dimension. The main characteristic
material constants (i.e., viscosity and modulus of elasticity) are also values of a
different dimension. The approach taken to combine elastic and viscous charac
teristics of a material for description of its viscoelastic properties is worth a spe
cial discussion because it leads to various models of a viscoelastic body.
Viscoelastic behavior can be considered as a slow (or delayed) development of
stresses and deformations in time, and this delay must not be confused with in
ertial effects also characterized by a specific lag time. A very important, al
though not explicit, word in the last sentence is “slow”. In order to discover
viscoelastic effects in regular liquids, we need to use ultrahigh frequencies
(characteristic time of an experiment in this case is about 10
7
s), whereas time
delay effects, in deformations of concrete rods and plastic tubes under pressure,
A. Ya. Malkin 245
require years of observation (characteristic time is about 10
8
s). Moreover, one
can treat deformations of stones as a very slowprocess, realizing that it requires
geological periods of time (characteristic time is of the order of 10
17
s; as we know
only the Lord has enough time to observe it).
The dimensionless criterion called the Deborah Number, De, was introduced
to be a measure of a ratio betweencharacteristic time of observation, t
obs
, and the
time scale of inherent processes in a material, t
inh
. Then
De = t
obs
/t
inh
The physical meaning of the value t
inh
is not identifiedhere, andinfact, it candif
fer. In a general sense, t
inh
characterizes the rate of inherent rearrangement of
the material structure. Since the level of structure organization, its rupture and
restoration can vary, we can find very different values of characteristic times for
the same material. Therefore, inprinciple, different values of the DeborahNum
ber are expected to exist.
The Deborah Number is especially important for viscoelastic phenomena be
cause they always proceed in time. Since the time interval is very wide, we must
encounter a situation when the Deborah Number is of the order of 1, i.e., an ob
server can “feel” that something happens with (or inside) a material. All this
means that complete description of viscoelastic phenomena includes experi
ments which must occupy no less than 15 decimal orders along the time scale.
Certainly, in the majority of cases, this is not very realistic. Therefore, two gen
eral approaches are usually taken to investigate viscoelastic phenomena:
• The measurement is done in a limited window along the time scale (for ex
ample, from10
1
to 10
3
s) and the experimental data extrapolated beyond the
borders of the window
• Special methods are used to accelerate (or decelerate) viscoelastic processes
and then empirical (or semitheoretical) approaches applied to modify the
timescale. For example, one may increase temperature to accelerate the
process. Then, it is assumed that the change in temperature is equivalent to
some change in the timescale (for example, what occurs at 100
o
C in 10 s re
quires 10
4
s at 20
o
C).
Both general approaches are empirical, and even in the best case, if they are
basedonsome theoretical ideas, they may or may not be correct. Besides, any ex
perimental data includes a scatter of points due to unavoidable errors of mea
246 Viscoelasticity
surement. The scatter of predictions (extrapolations) fromthis notideallyclear
window, with dispersed field points, is increasingly wider the farther we depart
fromthe borders of the window. It is thus rather dangerous to make far extrapo
lations, even though it is very attractive to observe deformations during 10 h
and predict further development of deformations for 10 years.
Viscoelastic phenomena belong to the fundamental rheological effects describ
ing the relationship between stresses and deformations. A general theory of
viscoelasticity is thus based on threedimensional analysis and consideration of
concepts as tensor values. Quite adequate understanding of basic ideas of
viscoelasticity is available for unidimensional deformations. Especially, it is
true, for small deformations when nonlinear effects of any kind do not appear.
In this case, it is not the mode of deformations which is important. That is why,
in the following Sections of this Chapter, discussion of simple deformations and
stresses does not identify the geometrical mode of deformation.
In specialized books, one can find a very rigorous and complete account of the
theory of (linear) viscoelasticity. The first comprehensive account of the linear
theory of viscoelasticity was published by B. Gross,
1
followed by several books
containing mathematical foundations and main results.
24
There are also some
textbooks containing not only main results of phenomenological theory but also
numerous ideas concerning its physical meaning and illustrating applica
tions.
57
It is now a homogeneous theory, based on solid mathematical back
ground, containing all necessary theorems and answers to pertinent questions.
However, following the line of this book, we do not attempt to prove statements
of the theory and conclusions discussed below. The major points −physical ideas
used in the theory, definitions, main results and relationships, not requiring
high mathematical analysis −are included for the practical purpose of their ap
plication in observation of material behavior.
Inorder to complete this introduction, it is worthmentioning that those profes
sionals who know the theory of electrical networks may notice that ideas, con
clusions, and relationships of the theory of viscoelasticity can be restructured
into terms of electrical networks by simple substitution of symbols. The same is
true for the theory of dielectric properties of materials. The same mathematical
structure of the theory is used, even though the physical objects differ.
A. Ya. Malkin 247
7.2 DEFINITIONS
This Section is devoted to the quantitative theory of effects briefly described in
Chapter 4.
Three fundamental experiments form the basis for the discussion:
• creep
• relaxation
• periodic deformations.
It is possible to discuss any other timedependent stress or/and deformation
modes, but these three are the simplest, and they allow us to define the main
concepts used for description of viscoelastic effects.
7.2.1 CREEP
At constant stress, σ
o
, applied at initial time (t = 0), slow(or delayed) develop
ment of deformations, ε(t), is observed, and this phenomenon is called creep.
The function ε(t) can be considered as consisting of three components:
ε ε σ σ
η σ
σ (t) = (t, ) + (t, ) +
t
( )
o o o
o
o
Ψ [7.1]
whereε
o
is an instantaneous deformation, Ψ(t, )
o
σ a function describing delayed
development of deformations, η σ ( )
o
viscosity, which (in a general case) can de
pend on stress, t current time.
Another form of Eq 7.1 is
η
σ
σ σ
η σ
(t)
= I(t) = I ( ) + (t, ) +
t
( )
o
ψ [7.2]
where the value I(t) is called compliance, I
o
an instantaneous compliance, and
ψ(t) a creep function. Subscript zero at σ is omitted in this equation.
As pointed out above, in formulating Eqs 7.1 and 7.2, the type of deformation
(extension, shear, and so on) is not specific but it must be accepted that deforma
tion is unidimensional.
A material is called linear viscoelastic if material parameters I
o
, ψ(t), and η
do not depend on stress; in the opposite case, material has nonlinear
viscoelastic behavior.
248 Viscoelasticity
It is necessary to separate two main cases shown in Figure 4.20:
• if ηis unlimitedly high, the last member in Eq 4.2 is absent and we deal with
a solid viscoelastic body. For linear viscoelastic solids, the value
ψ ψ → ∞
∞
= (t ) is limited and the sum
I = I +
o ∞ ∞
ψ [7.3]
is called equilibrium compliance.
• For viscoelastic liquids (curve 2 in Figure 4.20), deformation increases un
limitedly due to the linear (in time) increase of input of the last item in Eq
7.2. For viscoelastic liquids, equilibrium compliance equals zero.
Accelerated growth of deformation in creep (as shown by the curve 3 in Figure
4.20) is characteristic for nonlinear viscoelastic behavior and acceleration
starts at lower deformations.
Measurements of creep in longterm loading of materials are widely used for
many fabricated goods and parts of machinery, continuously exploited under
stress; for example, pipes for transporting gases under pressure. In all these sit
uations, creep has a detrimental effect on applied properties of materials. How
ever, in technological practice, creep is used as a method to produce orientation
in drawing of fibers, films, and so on, with posterior fixation of the oriented
state.
7.2.2 RELAXATION
At constant deformation, ε
o
, set at some initial moment of time, t = 0, we can
observe slow decay of stresses in time σ(t). This phenomenon is called relax
ation. The function σ(t) can be presented as consisting of two components
σ ε ε ε (t) = (t, ) + E ( )
o o o
Φ
∞
[7.4]
where Φ(t, )
o
ε is a function describing decay of stresses and E
∞
represents a re
sidual (nonrelaxing) or equilibrium component of stress.
Another form of Eq 7.4 is
σ
ε
ε ε
(t)
= (t, ) + E ( )
o
φ
∞
[7.5]
A. Ya. Malkin 249
where φ(t, ) ε is a function of stresses, called relaxation function (sometimes
this function is called relaxation modulus) and E
∞
is called an equilibrium
modulus.
Amaterial is called linear viscoelastic if φ(t) and E
∞
do not depend oninitial de
formation, ε; in the opposite case, material exhibits nonlinear relaxation. As a
rule, even with nonlinear behavior, E
∞
does not depend onε, but the rate of re
laxation represented by the function φ(t) does.
Similar to creep, it is reasonable to separate two main cases:
• if E = 0
∞
material is a viscoelastic liquid
• if E 0
∞
> , it means that a material can support stresses and therefore it is
considered a viscoelastic solid. In the latter case, the value
E = (0) + E
o
φ
∞
[7.6]
is called initial (or instantaneous) modulus.
Stress relaxation is a very important phenomenon in technological practice. If
it occurs with too slowa rate, the material is capable of storing residual (frozen)
stress, and this effect strongly influences its quality. Arapid relaxation can also
have adverse effect in use of some materials. For example, seals should exclude
gas or liquid leakages in equipments working under pressure. This can only be
achieved if a seal is continuously stressed during exploitation; relaxation leads
to loss of close contact between a seal and a solid wall of an apparatus.
7.2.3 PERIODIC OSCILLATIONS
It is the third well defined regime of deformations. The formof timedependent
periodic deformation can be arbitrary but the theory deals with harmonic oscil
lations. It is quite natural because a signal of any arbitrary form can be ex
panded into Fourier series to form a harmonic function.
For mathematical convenience, periodic signals can be written in complex ex
ponential functions exp(iωt) using Euler’s rule:
e t i t
i t ω
ω ω · + cos sin
It can be assumed that stress, σ(t), changes as
σ σ
ω
(t) = e
o
i t
[7.7]
250 Viscoelasticity
where σ
o
is an amplitude of stress, and ωits frequency of oscillations.
One may expect that deformations will change periodically, and in the first ap
proximation, ε(t) is described by a harmonic function with some delay with re
spect to σ(t). Then
ε ε
ω δ
(t) = e
o
i( t )
[7.8]
where ε
o
is an amplitude value of deformations and δ the phase angle (i.e., a
value characterizing the phase difference in oscillations of stresses and defor
mations); this value is also called loss angle and the physical meaning of this
term is discussed below.
If deformation, not stress, is a preset function, i.e.
ε ε
ω
(t) = e
o
i t
[7.9]
then stress is changing according to the equation
σ σ
ω δ
(t) = e
o
i( t+ )
[7.10]
Certainly, Eqs 7.9  7.10 are equivalent to Eqs 7.7  7.8.
Now, let us introduce the main parameter used to characterize viscoelastic
properties of a material measured by periodic oscillations. It is a dynamic
modulus of elasticity, E*, determined as
( )
E*= isin
o
o
σ
ε
σ
ε
δ δ · +
o
o
cos [7.11]
It is evident that E* is characterized by two parameters: its absolute value
E =
o
o
o
σ
ε
[7.12]
and phase angle, δ.
Both factors can depend on frequency and (in principle) on amplitude of defor
mation. For a linear viscoelastic body, the amplitude dependencies of E
o
and
A. Ya. Malkin 251
δ
δ are absent, which is an additional definition of linear viscoelastic behavior.
Dynamic modulus can be represented by two elements
E* = E + iE ′ ′′ [7.13]
where
E = cos ; E = sin
o
o
o
o
′ ′ ′
σ
ε
δ
σ
ε
δ [7.14]
These parameters are called real and imaginary components of dynamic
modulus, respectively, or E′ is calledstoragemodulus andE′ ′ loss modulus.
Absolute value of dynamic modulus is expressed through E and E ′ ′ ′ as
E =[(E ) + (E ) ]
* 2 2
1 2
′ ′ ′ [7.15]
Instead of E
*
and its components E and E ′ ′ ′, their reciprocal values can also be
used. They are called dynamic compliance
I = I iI
*
′ − ′ ′ [7.16]
determined as
I = cos ; I = sin
o
o
o
o
′ ′ ′
ε
σ
δ
ε
σ
δ [7.17]
The relationship between complex modulus and complex compliance is sim
ple and evident
E I = 1
* *
[7.18]
and relationships between components of E* and I* are established from
Eq 7.18 according to the rules of operation with complex numbers. They can be
written as
252 Viscoelasticity
E =
I
[(I ) + (I ) ]
; E =
I
[(I ) + (I ) ]
2 2
1 2 2 2 1/ 2
′
′
′ ′ ′
′ ′
′ ′
′ ′ ′
[7.19]
and vice versa:
I =
E
[(E ) + (E ) ]
; I =
E
[(E ) + (E ) ]
2 2 1/ 2 2 2 1/ 2
′
′
′ ′ ′
′ ′
′ ′
′ ′ ′
[7.20]
The last useful final expression in the theory of periodic oscillations is derived
from Eqs 7.14 and 7.17. It connects loss angle with components of dynamic
modulus and compliance:
tan =
E
E
=
I
I
δ
′ ′
′
′ ′
′
[7.21]
When liquids are studied by a method of periodic oscillations, sometimes it is
more convenient to use rates of deformation rather than deformations them
selves. If ε(t) is changing in accordance with Eq 7.8 then
& ε
ε
ε ω ωε
ω δ
=
d
dt
= i e = i
o
i( t )
A new parameter, characterizing viscoelastic properties and defined as regu
lar viscosity by the ratio of stress to rate of deformation, can be introduced. This
parameter is called dynamic viscosity and is expressed as
η
σ
ε
σ
ε ω
δ δ η η *= = (sin icos ) =
o
o
&
− ′ − ′ ′ [7.22]
where
η
σ
ε ω
δ
ω
η
σ
ε ω
δ
ω
′
′ ′
′ ′
′
= sin =
E
; = cos =
E
o
o
o
o
[7.23]
A. Ya. Malkin 253
Any pair of the aboveintroduced parame
ters is a complete measure of viscoelastic
properties of a material. It can be E′ and E′ ′
(or E′ and tanδ), or I′ and I′ ′ or η′ and η′ ′. All
other parameters can be calculated fromany
pair by means of simple algebraic operations
written above.
Concepts and definitions discussed above
can be visually interpreted by the graph
(Figure 7.1). Let deformations and stresses
be depicted by vectors with their length
equal to their amplitude values, 
o
ε and 
o
σ ,
respectively. Vector of deformation rate is
also given. Coordinate axes are formed by
real and imaginary numbers. The angle be
tween vectors of deformation and stress
equals the loss angleδ. Let all vectors in Fig
ure 7.1 rotate counterclockwise with angu
lar velocity ω. It means that the angle
betweenthe vectorσ
o
and abscissa equalsωt,
and between the vector ε
o
and abscissa is (ω δ t − ).
This figure allows for the following interpretation of the main parameters con
sidered in the theory of viscoelasticity. If we project the vector of stress onto the
vector of deformation, the value of σ δ
o
cos and the ratio of this projection to the
length of the vector of deformation gives the real component of dynamic modu
lus, E′. If we take the projection of σ
o
onto the direction perpendicular to the vec
tor of deformation and calculate the ratio of this projection (equal to σ δ
o
sin ) to
the length of the vector of deformation, the imaginary part of dynamic modulus,
E′ ′, is received.
If we project the vector of deformation onto the vector of stress and onto the
perpendicular direction to find the ratios of lengths, the definition of I′ and I′ ′ is
obtained. Then the analogous procedure with the vector of rate of deformation
leads to the components of dynamic viscosity.
The graphic interpretation of oscillatory measurements allows one to treat lin
earity of viscoelastic behavior for a linear viscoelastic material:
• by changing the length of one of the vectors in Figure 7.1, all other vectors
254 Viscoelasticity
Figure 7.1. Graphic interpretation
of osci l l atory measurements:
scheme illustrating interrelations
of al l mai n parameters of
viscoelastic behavior and their defi
nitions.
change proportionally to the first
• the angle between stress and deformation vectors does not depend on their
lengths and does not change during rotation of all vectors at any angular ve
locity.
One more geometrical interpretation of viscoelastic behavior, very useful and
utilized in practice, can be obtained from rearrangement of Eqs 7.7 and 7.8 and
by excluding time as a parameter of these equations. The direct relationship be
tween stress and deformation then has the following form:
σ
σ
ε
ε
δ
σ
σ
ε
ε
o
2
o
2
2
o o
+ = sin + 2

.
`
,

.
`
,

.
`
,

.
`
,
cosδ [7.24]
This equation is that of an ellipsis.
The following designations can be introduced in order to simplify the interpre
tation of experimental results:
x= ; y =
o o
σ
σ
ε
ε
Then Eq 7.24 can be written as
x + y = sin + 2xycos
2 2 2
δ δ [7.25]
The characteristics (ellipsis) described by Eq 7.25 is drawn in Figure 7.2. Calcu
lations show that the area of the ellipsis A is
A = sin
o o
πε σ δ [7.26]
i.e., the area of the ellipsis is proportional to the amplitude values of stress and
deformation and depends on loss angle, δ.
There are two limiting cases important for further interpretation:
• if δ π = 2, then Eq 7.25 has the form:
x + y = sin
2 2 2
δ
it means that an ellipsis degenerates into a circle;
A. Ya. Malkin 255
• if δ = 0, then Eq 7.25 degenerates into
x = y
which is an equation of a straight line.
Graphic interpretation of stressvsdeformation dependence in the form of el
lipsis allows one to make some comments concerning inputs of elastic and
dissipative components in deformation of viscoelastic material. For this pur
pose, let us calculate the work, W, produced during a cycle of deformation of a
viscoelastic body. This work is found as
W = (t)d
0
T
∫
σ ε [7.27]
where T= 2π ω is a duration of an oscillation cycle.
Direct calculations show that the work, W, is
W = sin
o o
πε σ δ [7.28]
The identity of expressions in Eqs 7.26 and 7.28 is obvious and gives the inter
pretation of the area of ellipsis in Figure 7.2 as the work produced during an os
cillation cycle. Certainly, there is no elastic (stored) energy when a cycle is
completed, because otherwise an unlimited increase in stored energy fromcycle
to cycle would be observed, which is physically impossible. That is why the en
ergy calculated fromEq 7.28 reflects the work dissipated during a cycle of oscil
lation. The ellipsis, as in Figure 7.2, is called a hysteresis loop because it
represents a delayed part of deformation.
Eq 7.28 allows one to propose the interpretation of a physical meaning of com
ponents of dynamic modulus andcompliance. If we substitute expressions for E′ ′
by I′ ′, the following equation is obtained:
W = E = I
o
2
o
2
πε πσ ′ ′ ′ ′ [7.29]
Both values, E and I ′ ′ ′ ′, are measures of energy dissipation during periodical os
cillations.
It is also possible to show that real components of dynamic modulus and com
pliance, E and I ′ ′, are measures of elasticity because energy stored (and then re
256 Viscoelasticity
turned) duri ng the cycl e of osci l l ati on i s
proportional to them.
The loss angle can be found fromFigure 7.2 by the
following simple method. The area of a rectangle
circumscribed around an ellipsis is equal to 4
o o
σ ε .
The ratio of areas of an ellipsis to a circumscribed
rectangle equals sinδ/4. Then it is possible to find
the loss angle from this ratio without the measure
ment of amplitudes of stress and deformation. This
approach is used in some standards, and instru
mental measurements were introduced in studies
of damping characteristics of rubbers and rubber
compounds. Hysteresis loop surface area (see Fig
ure 7.2) is a measure of mechanical losses on defor
mation.
Now, we cancome backto two limiting cases of the values ofδ mentionedabove.
If δ π · 2and sinδ = 1, the energy dissipation is at its maximum, typical for liq
uidwithout any elastic properties. If δ =0 andsinδ =0, there is no energy dissipa
tion, corresponding to the other limiting case of an elastic material without
viscous losses. In all other situations, intermediate cases are met in which the
value of the loss angle characterizes the ratio of viscoustoelastic properties in
viscoelastic materials. By decreasing δ, and consequently decreasing viscous
losses, material transits from pure viscous to pure elastic.
In real practice, viscoelastic materials are in the form of springs, rings, and so
on. Engineering constructions must be as highly elastic as possible (losses must
be low). Shockabsorbers, sound isolators, and materials for many other similar
applications must possess a high dissipative function, meaning that the loss an
gle of such materials must be as close to π/2 as possible.
The aboveformulated functions are used to describe viscoelastic effects and
characterize properties of real materials. However, it is necessary to emphasize
that the definition of all these functions implies that they must be defined (mea
sured) inthe range of their arguments (time or frequency as a value reciprocal to
time) fromzero andto infinity. It already has beenmentionedthat this is unreal,
and such a requirement is the main problem in practical applications of the
viscoelasticity theory. It is not a formal point but a serious physical limitation of
the theory. It is easy to write equations including these limits, and below, many
A. Ya. Malkin 257
Figure 7.2. Ellipsis in
stress  deformation coor
dinates as a representa
ti on of vi scoel asti c
properties of material.
equations of this kind are presented, including the aboveintroduced parame
ters, because they are frequently used in the theory of viscoelasticity. At the
same, it is very difficult to use equations in practice because input of some
viscoelastic functions (creep, relaxation, dynamic modulus) beyond the limits of
their direct measurement (beyond anexperimental “window”) canlead to uncer
tain errors in predicting deformation behavior of a real material. We shall re
visit this problem in the following sections of this chapter.
7.3 PRINCIPLE OF SUPERPOSITION
The general theory of viscoelasticity is designed to answer two related ques
tions:
• either functions, introduced for formal description of deformations or
stresses in the fundamental experiments (creep, relaxation, periodic oscilla
tion), are independent characteristics of material or they are inherently con
nected to each other
• if one or some basic functions of viscoelastic material are known (have been
measured), can one describe its deformationvsstress behavior in any arbi
trary mode of deformation (for example, find evolution of deformation for ar
bitrary history of loading)?
The answer to these questions is the main content of the theory of
viscoelasticity. And this answer is: “yes”, all fundamental functions are inher
ently related to each other, and “yes” to the second question means that we can
describe deformational behavior of material if at least one basic viscoelastic
function has been measured beforehand.
Both positive answers are founded based on the principle of linear super
position of stresses and/or deformations. This principle was formulated by
Boltzmann.
811
The concept may have different forms, but the basic idea is re
lated to the mutual independence of all consequent events happening to the ma
terial. In fact, it means that all materials are sufficiently weak, therefore they
cannot change the mode of reaction to an external action. The material reacts to
the next action as if no former action took place. In other words, the structure
and properties of material are not changed, regardless of its deformation, and
the last statement is a real physical meaning of the Boltzmann Principle.
Now, let us write the abovestated concept in the form of mathematical sym
bols. Let the initial stress, acting fromthe moment t =0, be equal toσ
o
. Then, de
formations change according to Eq 7.2. At some point of time, t′, let stress change
258 Viscoelasticity
by ∆σ. The principle of linear superposition assumes that in this case, deforma
tion changes accordingly:
ε σ ϕ
η
σ ϕ
η
(t) = I + (t) +
t
+ I + (T t ) +
t t
o o o
]
]
]
− ′
− ′
]
]
]
∆
Stress can change at any given time which follows. For any such moment of
time and any corresponding change of stress, one can add an independent item
in the last equation for ε(t).
Certainly, stress can change continuously, and bearing this in mind, we come
to the final integral (instead of sum) formulation of the Boltzmann principle of
linear superposition:
ε
η
σ (t) = I + (t t ) +
t t
d
0
t
o
∫
ψ − ′
− ′
]
]
]
[7.30]
or
ε
σ
η
(t) =
d
dt
I + (t t ) +
t t
dt
0
t
0
∫
′
ψ − ′
− ′
]
]
]
′ [7.31]
The analogous line of arguments can be used to describe changes in deforma
tion, and in this case, Eq 7.5 is a startingpoint. The final result is quite similar
to Eq 7.31, and can be written as
σ
ε
ϕ (t) =
d
dt
[ (t t ) + E ]dt
0
t
∫
′
− ′ ′
∞
[7.32]
The pair of symmetrical Eqs 7.31  7.32 is called the BoltzmannVolterra
equations.
12,13
They are the mathematical formulation of the principle of lin
ear superposition.
It is possible to illustrate the behavior of viscoelastic material according to the
principle of superposition by the following example for elastic recoil (retarda
tion) after forced deformation of a body.
A. Ya. Malkin 259
Let the history of deformations be as shown in Figure 7.3a: the external force
created deformation, ε
o
, and then (very rapidly) the same deformation but with
the opposite sign, 
o
ε . When the force was acting during two short periods of
time, one could neglect partial relaxation at deformationsε ε
o o
and − . The ques
tion is: what happens if, at the moment A, the external force is removed? Ideal
elastic body immediately returns to its initial state, as shownby the vertical line
fromthe point Ain Figure 7.3b. The behavior of viscoelastic body is quite differ
ent, as illustratedby the line ABCinFigure 7.3c. The first part of this line, AB, is
retardation from the second deformation, 
o
ε , not to zero but to a state deter
mined by the first deformation, ε
o
. Only after that slow (delayed) action, a re
turn to the zero state occurs.
Another very interesting (and important for technological applications) exam
ple of influence of deformational prehistory on the behavior of a material is re
lated to the processing of polymers (thermoplastics and rubber compounds).
During extrusion of continuous profiles, a molten material moves between a
screwanda barrel of anextruder, thenit passes transient channels. Finally, it is
shaped in an outlet section of a die. It would be desirable that the shape of a final
profile is equivalent to the shape an outlet section of a die. On the contrary, the
material continues to react to all deformations whichtookplace before the outlet
sectionof a die. As a result, distortionof its shape occurs; therefore, the final sec
tion of a part can be very different than expected. The distortions can be so se
vere that “melt fracture” (shown in Figures 4.14 and 4.15) is observed.
These and many other examples are characteristic for technological practice.
Viscoelastic materials have fading memory of the history of previous deforma
260 Viscoelasticity
Figure 7.3. Deformation history (a) and the reaction (from the point A when outside force is re
moved) of ideal elastic (b) and viscoelastic (c) materials.
tions. Inthis sense, the integrals 7.31 and 7.32 are called hereditary integrals
because they summarize events which took place before the current moment of
time and are responsible for the stress (or deformation) state of a material at the
current moment.
The relaxation functionφ(t) is a decreasing function. Therefore, its values are
higher when the argument is smaller. It means that the changes of deformation,
which happened earlier, influence stress in lesser degree than later changes. In
the first case, the value of the argument (tt′) in Eq 7.32, for the fixed moment of
time, t, is smaller than for events which happened later because values of t′ are
smaller. Inother words, a material continuously “forgets” what happenedbefore
and therefore integrals in Eqs 7.31 and 7.32 forma model of material with “fad
ing memory”.
It is interesting to outline the limiting cases. They are:
• liquid which “forgets” everything immediately (energy of deformation com
pletely dissipates); in this case, the integral 7.32 transforms to the New
tonStokes Law
• solid which “remembers” everything (energy of deformation is completely
stored), and in this case, the integrals 7.31 and 7.32 transform to the Hooke
Law.
Both Eqs 7.31 and 7.32 contain deformation and stress, and each of them can
be treated as anequationeither of stress or deformation. Eq 7.31 determines the
development of deformations for known evolution of stresses. It can be consid
eredas anintegral equationforσ(t) if the functionε(t) is known. The same is true
for Eq 7.32. Therefore, it is possible to exclude these functions by substituting,
for example, the functionε(t) fromEq 7.31 to the right side of Eq 7.32. After some
formal mathematical rearrangements, the relationship between rheological pa
rameters does not contain either σ(t) nor ε(t). The resulting equation includes
creep and relaxation functions in the following form:
E I + I (t) + E
t
+ (t) + (t )
1
+
d (t t
d(t t )
o o ∞ ∞
ψ
]
]
]
′
ψ − ′
− ′
ϕ
η
ϕ
η
]
]
]
′
∫
dt = 1
0
t
[7.33]
where E
∞
is an equilibrium modulus, I
0
an instantaneous compliance, ηviscos
ity, φ(t) a relaxation function, and ψ(t) creep function.
Eq 7.33 shows that the relaxation and creep functions are not independent but
related to each other by the integral equation. If one of these functions is known
A. Ya. Malkin 261
(measured, calculated, assumed), the other can be found from Eq 7.33. This
equation formally, and quite rigorously, confirms the aboveformulated state
ment that the behavior of material, in different modes of deformations, is gov
erned by the same inherent properties.
Eqs 7.31 and 7.32 give mathematical ground for calculation of stressvsdefor
mation relationship at any arbitrary path of material loading. The only essen
tial limitation in application of these equations is the requirement of linearity of
rheological behavior of a medium, i.e., independence of all material constants
and functions entered to these equations (instantaneous compliance, equilib
rium modulus, viscosity, relaxation and creep functions) on stresses and defor
mations.
Certainly, Eqs 7.31 and 7.32 are rheological equations of state for viscoelastic
materials. It is necessary to remember that everything discussed above is re
lated to “a point” in the sense as adapted for a Newtonian liquid and a Hookean
solid and in general for any rheological equation of state. In order to find
stressdeformation distribution throughout a body, one must combine these
equations with equilibriumconditions (equations of conservation, introduced in
Chapter 2) andappropriate boundary conditions as suggestedinChapters 5 and
6 for any liquid and solid.
7.4 RELAXATION AND RETARDATION SPECTRA
Relaxation, ϕ(t), is a decreasing (at least not increasing) function of time. As a
first approximation, it is reasonable to estimate it by an exponential function:
ϕ
θ
(t) = E e
o
t/
[7.34]
where E
o
is a instantaneous modulus andθ is a value calledarelaxationtime.
Relaxation process is described by a single exponential function called
Maxwell (or Maxwellian) relaxation. However, it is a rather rough approxima
tion and it can be improved by increasing the number of exponents, i.e., by ex
pansion of ϕ(t) into a sum of N exponents:
ϕ
θ
(t) = E e
i =1
N
i
t/
i
∑
[7.35]
262 Viscoelasticity
E = E
o
i =1
N
i ∑
where E
i
are called partial moduli, and θ
i
are the set (or a spectrum) of relaxation
times.
Such spectrum can be called discrete and
can be drawn by a set of lines as in Figure
7.4, where each value of E
i
(length of a line)
is put in correspondence to its argument
equal toθ
i
. In the limiting case, the lines in
Figure 7.4 can fill all the graph if they are
situated very close and their tops form a
continuous curve. In this limiting case, we
have the transition from the sum in Eq
7.35 to the integral
ϕ θ θ
θ
(t) = F( )e d
0
t/
∞
∫
[7.36]
where the value F( )d θ θ plays a role of a partial modulus as in Eq 7.35 and the
function F(θ) is called a relaxation spectrum or a distribution of relaxation
times.
There is a mathematical theorem stating that any decreasing function (in our
case, the relaxation function, ϕ(t)), of any kind can be represented by its expo
nential image, i.e., by the integral (Eq 7.36). This statement leads to the conclu
sion that there is an unambiguous correspondence between any relaxation
function, ϕ(t), and the relaxation spectrum, F(θ).
In principle, a relaxation spectrumcan be found as a solution of the integral in
Eq 7.36. Certainly, it is always possible to know the analytical form of the func
tion ϕ(t) in its full interval from 0 to ∞. It appears simple in a theoretical ap
proach, but not so easy in treatment of experimental data.
There are two reasons complicating a problem of the transition from experi
mental points to solutionof the integral Eq 7.36. Bothreasons already have been
mentioned above: the first is an uncertainty in behavior of an experimental
functionbeyond the borders of measurements (close to zero and at highvalues of
A. Ya. Malkin 263
Figure 7. 4. Discrete relaxation
spectrum.
the argument, at t → ∞), and the second concerns the natural scatter of experi
mental points, which makes the analytical approximation of these points, and
extrapolation beyond the experimental window, an ambiguous procedure.
It is very important to knowthe relaxationspectrumbecause inmany theoreti
cal investigations a relaxation spectrum, is directly related to molecular move
ments and thus to molecular structure of matter. Therefore, many different
methods were proposed which give a solution of this problem. Below, comments
are included concerning their validity.
7.4.1 CALCULATING CONTINUOUS SPECTRUM
The method is based on direct solving of Eq 7.36. There are two possible ways
to do so. The first consists of analytical approximation of experimental points by
appropriate formula and direct solving of Eq 7.36 using numerous published ta
bles of conversion of exponential images. The error of approximation must be
lower than an experimental error, and many such analytical approximations
are possible. Each of them gives a different spectrum.
16
If the error of approxi
mation is sufficiently low, it does not yet imply that the error of a calculated
spectrum is acceptable.
It is also possible to use the second, rather old, method
6
of finding a rough solu
tion of Eq 7.36. For this purpose, one can substitute an exponential function in
Eq 7.36 by its approximate expression:
exp(t / ) 1 at t / <1; t < θ θ θ ≈
exp(t / ) at t / 1; t θ θ θ · > > 0
The idea of this (first order) approxima
tion is seen from Figure 7.5. The continu
ous exponential curve is changed by an
abrupt step. Eq 7.36 becomes:
ϕ θ θ
θ
(t) F( )d ≈
∞
∫
[7.37]
In fact, it means that a term on the right
side of Eq 7.36 is omitted on the basis that
264 Viscoelasticity
Figure 7.5. Stepwise change of expo
nential functionto calculate a spectrum
(first approximation).
the exponential decay will suppress the input fromthe functionF(θ), assumed to
be rather low. The error of this approximationis unknown. Due to this process, a
very simple formula for calculation of F(θ) is obtained by differentiating both
sides of Eq 7.37 by the lower limit of the integral:
F( ) =
d (t)
dt
at t = θ
ϕ
θ − [7.38]
The idea of this method can be used for higher approximations but the same
main disadvantages of uncertain errors still exist.
7.4.2 CALCULATING DISCRETE SPECTRUM
The practice of treating real experimental data of rheological investigations
shows that, in fact, any relaxation curve (decay of stresses) can be approximated
by the sum of 45 or (in the worst case) of 78 exponential items. A very limited
number of relaxation times is thus needed to describe experimental points with
permissible error within scatter of measurements.
Standard computer procedures of minimizing an error in finding constants of
some analytical formula are also available. This problem was under discussion
fromthe beginning of applicationof the linear theory of viscoelasticity to real ex
perimental data and continues to be the focus of interest. The most important
goal is to minimize nonlinear functional errors to which numerous publications
were devoted.
1418
In this case, it is a sum of N exponents with unknown weights
E
i
and values of θ
i
. In this approach, one begins with N · 1 and increases the
number of exponents. Each step permits on to decrease the error of approxima
tion. The last stepandthe final number of exponents is whenanerror of approxi
mation becomes lower than permissible error of experiment.
In some theories, the set of relaxation times appears to be dependent but fol
lows the definite rule. For example, the rowof relaxation times obeys the follow
ing rule:
θ θ
i o
ni
=
where θ
o
and n are constants (e.g., n = 2) and i are integers (i = 0, 1, 2, 3...).
19
It
limits the possibility to vary the parameters of a relaxation spectrum because
there are only two independent parameters (θ
o
and n); moreover, since n is a re
sult of molecular model calculations it cannot be treated as a fully independent
A. Ya. Malkin 265
parameter. Now the relaxation function takes the following form:
ϕ θ (t) = E
i =1
i
ni
∞
∑
[7.39]
The procedure minimizes error of approximation but the set of constants under
search (E
i
) is different from the general case based on Eq 7.35.
According to this approach, it is irrelevant to search for a “true” number of ex
ponents (or relaxationtimes) ina discrete spectrumbecause the procedure of ap
proximationshould only be continued up to the limit of experimental error, after
which further effort is inconsequential. The minimal number of exponents
whichcorrectly (withinthe limits of experimental error) describe results of mea
surements should be used.
Discussion of the relaxation function, ϕ(t), can be almost repeated word for
word as regards the creep function, ψ(t). In the latter case, the resulting equa
tion is as follows:
ψ −
∞
∑
(t) = [I (1 e )]
i =1
i
t/
i
λ
[7.40]
or in the form of the continuous spectrum:
ψ −
∞
∫
(t) = ( )(1 e )d
0
t/
Φ λ λ
λ
[7.41]
where Φ(λ) is called a retardation spectrum or a distribution of retardation
times.
The introduction of the integral kernel in Eq 7.40 in the form (1 e
t/
−
λ
) instead
of e
t/ θ
is explained by the fact that ψ(t) is increasing, not decreasing (as ϕ(t)),
though its mirror reflection, or elastic recoil function, is also a decreasing func
tion, as is shown in Figure 4.20, curve 1.
The change of an exponent functione
t/ θ
for (1 e
t/ λ
) leads to small variations
in methods of approximation of spectrum. Instead of the step shown in Figure
7.5, one may write the following (first order ) approximate equalities:
266 Viscoelasticity
1 e 0 at t / <1; t <
t/
− ≈
λ
λ λ
1 e at t / 1; t
t/
− ≈ > >
λ
λ λ 1
Graphic interpretation of this approximation is essentially the same as in Fig
ure 7.5, withanexceptionthat the mirror reflectionof Figure 7.5 is considered.
Discussion in relation to a relaxation spectrum, including arguments concern
ing methods of its calculation, holds true for a retardation spectrum.
In real practice, the measurement of relaxation and retardation (or creep) is
performed for as wide a time range as possible to cover at least some decimal or
ders of the argument. It is analogous to determining a flowcurve (Chapter 5) ina
wide range of shear rates. The linear time scale is changed to logarithmic in or
der to make experimental results easier to visualize (the same method was used
for flow curves in Chapter 5). This conversion is expressed by the following for
mulas:
ϕ θ θ
θ
(t) = H(ln )e dln

t/
∞
∞
∫
[7.42]
and
ψ
∞
∞
∫
(t) = L(ln )e dln

t/
λ λ
λ
[7.43]
withthe following obvious relationships betweenlinear andlogarithmic spectra
H(ln ) = F( ) θ θ θ [7.44]
and
L(ln ) = ( ) λ λ λ Φ [7.45]
A. Ya. Malkin 267
The last problem to be discussed in this section concerns the interrelation be
tween distribution of relaxation and retardation times. They are not equivalent,
though certainly they both originate from the same molecular phenomena and
thus are closely related to each other.
The existence of interrelation between relaxation F(θ) and retardation Φ( ) λ
spectra can be proven if we take into account that F(θ) represents a relaxation
function, Φ( ) λ represents a creep function, and both are connected by Eq 7.33. It
is illustrated in Figure 7.6. One can expect that a relationship between spectra
F(θ) and Φ( ) λ also exists.
20
If one of the pair of spectra is continuous, the second one is also continuous,
thoughthey are not equivalent. If a relaxationspectrumis discrete, thena retar
dationspectrumis also discrete. Besides, there is aninteresting point rigorously
proven in the theory regarding correlation of numbers and positions of lines in a
pair of discrete spectra. In viscoelastic liquid (η< ∞ and G = 0
∞
), the number of
members (lines) in a relaxation spectrum is larger by one than the number of
members in a retardation spectrum, and the lines of a retardation spectrumare
arranged between the lines of a relaxation spectrum. For example, in
Maxwellianrelaxationthere is one relaxationtime (Eq 7.34) but the retardation
spectrumis empty (no lines) and deformationof a Maxwellianviscoelastic liquid
at constant stress occurs without delay. In a viscoelastic solid, the number of
lines in both spectra is the same.
7.5 DYNAMIC AND RELAXATION PROPERTIES  CORRELATIONS
The dynamic characteristics (components of dynamic modulus and compli
ance) can be correlated with the relaxation properties of material. Certainly, it
can be done based on the fundamental principle of linear superposition. In this
section, main theoretical results of correlations between dynamic and relax
ation properties are discussed.
The components of the dynamic modulus are expressed through a relaxation
function as
G ( ) = (t)sin tdt
0
′
∞
∫
ω ω ϕ ω [7.46]
268 Viscoelasticity
The inverse relationships, i.e., solution of Eqs 7.45 and 7.46, have the following
form:
G = (t)cos tdt
0
′ ′
∞
∫
ω ϕ ω [7.47]
For a relaxation function ϕ(t), which is calculated from components of the dy
namic modulus, it has a similar form:
ϕ
π
ω
ω
ω (t) =
2 G ( )
sin tdt
0
∞
∫
′
[7.48]
and
ϕ
π
ω
ω
ω (t) =
2 G ( )
cos tdt
0
∞
∫
′ ′
[7.49]
Two main conclusions can be drawn from Eqs 7.46 to 7.49:
• components of the dynamic modulus can be calculated if a relaxation func
tion was measured (and vice versa)
• accuracy of such calculations is limited by the need to find the integrals in
these equations in limits from 0 to ∞, and uncertain input of “tails" of func
tions on the right side of these integrals.
Analogous equations canbe established for the components of dynamic compli
ance. Rigorous calculations give the following results:
I ( ) =
t
cos tdt
0
′
∂ψ
∂
∞
∫
ω ω [7.50]
I =
t
sin tdt
0
′ ′
∂ψ
∂
∞
∫
ω [7.51]
A. Ya. Malkin 269
The inverse relationships for a creep
function can also be written. They are
quite analogous to Eqs 7.48 and 7.49, with
an evident change of components of modu
lus for compliance and relaxation function
for a derivative of a creep function.
The same conclusions apply to the possi
bility of a mutual correlation between dy
namic compliance and creep function, as
for the correlationbetweendynamic modu
lus and a relaxation function as discussed
above.
The main sense of all equations given in
this section is, first of all, to demonstrate
the existence of relationships for all
viscoelastic characteristics under discus
sion (they can be used for mutual calculations), and secondly, to emphasize the
fact that all these relationships are represented by the integral equations with
infinite limit, which complicates practical applications of these relationships.
Figures 7.6 and7.7 showthat components of dynamic modulus andcompliance
can also be expressed through relaxation (retardation) spectra. The equations
below give a final result for G
*
(ω):
E ( ) = F( )
( )
1+ ( )
0
2
2
′
∞
∫
ω θ
ωθ
ωθ
[7.52]
E = F( )
( )
1+ ( )
0
2
′ ′
∞
∫
θ
ωθ
ωθ
[7.53]
Analogous equations can be written for I ( )
*
ω , and they are
I ( ) = ( )
1
1+ ( )
d + I
0
2
o
′
∞
∫
ω λ
ωλ
λ Φ [7.54]
270 Viscoelasticity
Figure 7.6. Structure of interrelations
between relaxation and retardation
spectra.
I =
1
+ ( )
( )
1+ ( )
d
0
2
′ ′
∞
∫
ωη
λ
ωλ
ωλ
λ Φ [7.55]
All these relationships have a
structure very similar to the
equations discussed above.
They show that it is possible to
establish correspondence be
tween dynamic properties and
relaxation spectra, but real cal
culations are rather complex
because of integral equations
with infinite limits.
Inverse transforms of Eqs
7.52 to 7.55 cannot be ex
pressed in analytical form for
arbitrary dynamic functions. It
can be illustrated by constructing the first approximation formula related to re
laxation spectrum and dynamic modulus.
22,23
As in Figure 7.5, we change the
kernel in the equation for dynamic modulus stepwise:
( )
1+ ( )
0 at <
2
2
1
ωθ
ωθ
θ ω ≈
( )
1+ ( )
at
2
2
1
ωθ
ωθ
θ ω ≈ > 1
The meaning of this approximation is il
lustrated in Figure 7.8. Then, Eq 7.51
changes to
E F( )d
1
′ ≈
∞
∫
ω
θ θ
A. Ya. Malkin 271
Figure 7.7. Structure of interrelations between relax
ation characteristics of a viscoelastic material includ
ing dynamic modulus and compliance.
Figure 7.8. Stepwise change of the ker
nel in the integral equation for dynamic
modulus to calculate a spectrum (first
approximation).
After differentiating it by the lower limit of integral, the following approximate
equationfor calculating a relaxationspectrumby dynamic modulus is obtained:
F( )
dE ( )
d
at =
2
1
θ
ω ω
ω
θ ω ≈
′
Quite analogous equations can be written for all other dynamic functions un
der discussion. Their accuracy is limited by an uncertain input of the “tail” of a
function used for calculations which has been cut off because of change in the
kernel in the integral equation by a rather rough step approximation − a com
mon feature of all approximations used in solving integral equations applied in
the theory of linear viscoelasticity
Equations written in the last two sections and schemes in Figures 7.6 and 7.7
give the positive answer to the main question on the theory formulated above:
all viscoelastic characteristics of a material are related to each other and can be
mutually calculated. However, this answer is partially positive because of inevi
table complications of these calculations, due to the special form of equations
connecting all viscoelastic functions.
7.6 RELATIONSHIPS BETWEEN CONSTANTS
In the main definitions and in all equations of the theory of viscoelasticity
there are some constants representing limiting cases (at t = 0 and t → ∞) of
stresses and deformations. These constants are:
η viscosity at steady flow (constant when liquid is linear or Newtonian)
I
o
 instantaneous compliance
I
∞
 equilibrium compliance
E
∞
 equilibrium modulus
E
o
 instantaneous modulus.
Discussion below concentrates on establishing the relationships between
these constants and relaxation characteristics of a material, such as creep and
relaxation functions, and a relaxation spectrum. To begin, it should be repeated
that some of the constants are characteristics for either viscoelastic solid or
viscoelastic liquid, which causes relationships between the constants to be dif
ferent for these two types of viscoelastic materials.
272 Viscoelasticity
7.6.1 VISCOELASTIC SOLID
The definition of a solid is
1
= 0
η
It is a rather formal definition because material with viscosity of the order 10
20
Pa⋅s (inorganic glass) is a solid, though formally it is a liquid having very high
viscosity. Nevertheless, this formal definition is important for rigorous classifi
cation of viscoelastic materials.
Then, for a viscoelastic solid, when stress is preset:
I =
1
G
=
1
G + (0)
o
o ∞
ϕ
[7.56]
and
I = I + ( )
o ∞
ψ ∞ [7.57]
For a viscoelastic solid when deformation is preset:
E = I
o o
1
[7.58]
E =
1
I + ( )
= I
o
1
∞ ∞
ψ ∞
[7.59]
and
E E = (0) =
( )
I [I + ( )]
=
I I
I I
o
o o
o
o
−
ψ ∞
ψ ∞
−
∞
∞
∞
ϕ [7.60]
A. Ya. Malkin 273
7.6.2 VISCOELASTIC LIQUID
The definition of a liquid is
η< ; E = 0 ∞
∞
Then, one can derive the following relationships between the constants:
E = I = (0) = F( )d
o o
1
0
ϕ θ θ
∞
∫
[7.61]
All other relationships vanish because E
∞
= 0.
Two of the relationships listed above are of special interest: equation express
ing instantaneous modulus by “zero” moment and viscosity by “ first” moment of
a relaxation spectrum:
E = F( )d ; = F( )d
o
0 0
∞ ∞
∫ ∫
θ θ η θ θ θ [7.62]
Then, it is possible to determine a certain “average” relaxation time, θ
av
, as a ra
tio η/ E
o
θ
η
θ θ θ
θ θ
av
o
0
0
=
E
=
F( )d
F( )d
∞
∞
∫
∫
Certainly it is possible to define other characteristics of “averaged” relaxation
times, such as ratio of two consequent moments of a relaxation spectrum.
7.7 MECHANICAL MODELS OF VISCOELASTIC BEHAVIOR
Theory of viscoelasticity is treated above as a phenomenological generalization
of ideas concerning delayed effects in deformations or superposition of elastic
storage and viscous dissipative losses of energy during deformation. The con
cepts of relaxation or slow return to the equilibrium state and creep can also be
274 Viscoelasticity
introduced frommore general physical reasoning and illustrated by very visual
examples.
Let the state of a system be characterized by a certain parameter x and its
value corresponding to the equilibrium state by x
∞
. Then, let us consider the
possible reaction of a systemtaken out of its equilibriumstate. Asystemalways
tends to return to the equilibrium state. Let us assume, according to the
Maxwell fundamental idea, that the rate of an approach, from any arbitrary
state, to the equilibrium state is proportional to the degree of divergence from
the equilibrium.
In the language of mathematics, this concept can be written in the formof a ki
netic equation
dx
dt
=
1
(x x ) − −
∞
θ
where 1/θ is a kinetic factor, characterizing the rate of changes in the state of a
system.
The integral of this differential equation is
x= x e + x
o
t/ θ
∞
[7.63]
where x
o
is an initial value of x.
It is quite evident that if stress is substituted by parameter x, the equation de
scribes mechanical relaxation, withθ being a characteristic time of relaxation of
this process and x
∞
the residual stress, which equals zero for liquid.
Now, let us imagine a mechanical model constructed from a combination of a
spring and a plunger in a cylinder filled with a liquid (damper), with these two
elements connected in series (Figure 7.9). The spring is a model of an ideal
Hookean solid and its deformation is described by the equation
X =
F
E
H
where X
H
is a displacement of a lower end of a spring from the equilibrium
(nonloaded) state, Eis the modulus of a spring, and F is the force applied at the
bottom of the model, causing its deformation.
A. Ya. Malkin 275
A plunger moving in a cylinder filled with vis
cous liquid (damper) is a model of an ideal New
tonian liquid and its deformation is described
by the equation
&
X =
dX
dt
=
F
N
N
η
where dX
N
/dt is the rate of displacement of a
plunger, ηviscous resistance to a movement of
the plunger in the cylinder, proportional to vis
cosity of liquid, F the same force which caused
the deformation of the spring.
It is evident that the full displacement of a
lower point of the model inFigure 7.9 is a sumof
the two components: the displacement of the
bottom of a spring and the movement of a
plunger. It can be written as follows:
X= X + X
H N
and
& & &
X= X + X
H N
After substituting expressions for displacement of the elements of the model,
the equation for deformation of the whole model is obtained:
&
&
F
E
+
F
= X
η
[7.64]
Let us analyze the behavior of the mechanical model in Figure 7.9 (called
Maxwell model)when the step displacement is set up, or in other words, let us
find a relaxation function of this model. Integrating Eq 7.64 at the appropriate
boundary conditions gives
276 Viscoelasticity
Figure 7.9. Mechanical model of
Maxwellian relaxation: spring
and a plunger in a cylinder with
viscous liquid (damper), con
nected in series.
F(t) = X Ee
o
tE/ η
or
F(t)
X
= (t) = Ee
o
t/
ϕ
θ
[7.65]
where X
o
is an initial displacement of the bottom of the model, and θ η = E a
constant which can be called a relaxation time.
The complete equivalence of Eq 7.64 to expressions for relaxation of a liquid
having a single relaxation time (Eq 7.34) and the Maxwell concept of relaxation
as delayed approach to the equilibriumstate (Eq 7.63) are quite evident. That is
why the model showninFigure 7.9 is called the model of the Maxwell liquid. The
rheological equation of state, Eq 7.64, is called the equation of linear Maxwell
viscoelastic liquid.
The rheological properties of a linear Maxwell viscoelastic liquid are charac
terized by the following parameters: viscosity, η, instantaneous modulus, E, and
the components of dynamic modulus which are expressed as
G ( ) = E
( )
1+ ( )
; G = E
1+ ( )
2
2 2
′ ′ ′ ω
ωθ
ωθ
ωθ
ωθ
and
tan = ( )
1
δ ωθ
Certainly the mechanical model drawn in Figure 7.9 is a model of liquid be
cause equilibrium modulus is zero.
A creep function of a Maxwell liquid is described by the equation
ψ(t) =
(t)
=
1
E
+
t
o
ε
σ η
This equation shows that, when a constant stress is preset, a steplike defor
mation equals σ
o
E / , and there is no delay in deformation.
A. Ya. Malkin 277
The mechanical model, repre
sented inFigure 7.9, reflects the
viscoelastic behavior of a sin
glerelaxationtime liquid. In
line with phenomenological
general i zati on of a si n
gletimerelaxation in Eq 7.34
to the sum of exponents in
Eq 7.35, we can obtain the same
result using mechanical mod
els. This aim is reached by the
same method of summarizing
exponential items, as in Eq
7.35. Indeed, let us join in paral
lel a number of Maxwell models
with different values of parame
ters. Then, the relaxationprocess, inthis multirelaxationtime Maxwell model,
is described by Eq 7.35 with a set of relaxation times, having different value for
every branch of a generalized model.
The rheological behavior of the generalized model is described by an equation
of the differential type containing time derivatives of stress anddeformation(Eq
7.68).
Another way of constructing mechanical models consists in joining a spring
and a plunger moving ina cylinder withviscous liquid (damper), not inseries, as
in Figure 7.9, but in parallel, as shown in Figure 7.10. This model is called the
KelvinVoigt model. The mechanical properties of bothelements inthis model
are the same as in the Maxwell model, but, contrary to the latter (deformations
of the components are added), stresses acting in the branches of a model are
added. The following equation describes the rheological properties of the Kel
vinVoigt model:
E + = ε ηε σ & [7.66]
In the standard experiment, when σ σ = = const
o
, the following creep function
of the KelvinVoigt model takes place:
278 Viscoelasticity
Figure 7.10. Mechanical model of delayed (Kel
vinVoigt) creep: spring and a plunger in a cylinder
with viscous liquid (damper) connected in parallel.
ψ − (t) =
(t)
=
1
E
(1 e )
o
t/
ε
σ
λ
[7.67]
whereσ
o
E / is the initial deformation, andconsequently E
1
=I
o
is instantaneous
compliance, and λ η/ = E is a retardation time.
It can be easily shown that the KelvinVoigt model represents the viscoelastic
behavior of a solid, because the model conserves residual stresses equal to E
o
ε ,
whereε
o
is an instantaneous deformation. This model represents the properties
of a nonrelaxing body (relaxation time is equal to infinity).
Generalizing the serially joined elementary models, one obtains the model of
viscoelastic solid behavior with a set of retardation times. Creep of the
multiconstant KelvinVoigt model is described by Eq 7.40.
In a general case deformation properties of any mechanical model constructed
from the Maxwell and KelvinVoigt elements can be represented by the equa
tion:
n
N
n
n
n
m
M
m
m
m
A
d
dt
= B
d
dt
∑ ∑
ε σ
[7.68]
where the order (M and N) of sums in Eq 7.68 depends on the structure of a me
chanical model, and A
n
and B
m
are material constants of a model.
Thus, any mechanical model leads to the equation describing mechanical be
havior of a material by a differential equation and this is equation of state of
differential type, contrary to equationof state of integral type such as Eqs
7.31 and 7.32. It means that differential equations correspond to line (discrete)
relaxation spectra, while integral equations correspond to continuous spectra.
This difference is not very important because any discrete spectrum can be ap
proximated by a smooth curve and any continuous spectrum can be approxi
mated by a set of lines; nevertheless, this difference exists and can be used in
applications for real calculations.
Whether the model represented by Eq 7.68 corresponds to a viscoelastic liquid
or to a viscoelastic solid is determined by the junior member of the lefthand
sum. If this member is of the zeroth order, i.e., calculation of the sum starts
fromn = 0, it is a model of a solid. If the zeroth member is absent and the junior
member is of the first order (n=1), it is a model of liquid. For the Maxwell model,
A. Ya. Malkin 279
N = 1 (there is only one member in the leftside sum) and M = 1. For the Kel
vinVoigt model also, N = 1 (but we have two members in the leftside sum be
cause the junior member corresponds to n = 0) and M = 0 (only one member is
present in the rightside sum).
Varying the order of differential operators in Eq 7.68 and values of parameters
A
n
andB
m
, we are able to describe various special cases of viscoelastic behavior of
a material with any arbitrary relaxation properties. There is one fundamental
limitation: Eq 7.68 describes mechanical properties of a linear viscoelastic ma
terial and cannot go beyond this limit if some modification of the initial idea is
not introduced.
After the Maxwell and KelvinVoigt models were proposed, many attempts
were performed to apply models to explain the behavior of real physical sub
stances. Inthis approach, it was thought that the abovediscussed models repre
sent not only behavior but also molecular structure of a body. For example, in
considering relaxation properties of a very long (polymeric) molecular chain, it
was proposed that any part of such chain can be represented by the Maxwell
model.
Suchanapproachopens wide opportunities for constructing models of real ma
terials expressed by combinations of elementary Maxwell and KelvinVoigt
models. Though some of these structures are very attractive, it is, however, nec
essary to distinguish between models of a body structure and models of material
behavior, which are not the same (both are related to each other, not quite di
rectly and not in an obvious way). Any mechanical model is a model of behavior,
and the stressdeformation relationship, describing movement of elements of a
mechanical model, gives equations which can closely approximate deformation
behavior of material. The model can be very deceiving because a real body does
not consist of springs and dampers.
The equations of differential type, like any other rheological equations, are
written for a “point”. If deformations are small, time derivatives entering Eq
7.68 are only partial time derivatives and nothing more. If deformations become
large, it appears necessary to substitute ε in Eq 7.68 by some measure of large
deformationto use their time derivatives as discussed inChapter 3. This offers a
model of a viscoelastic mediumcapable of large deformations and leads to some
new rheological phenomena which can be treated as a weak nonlinear effect.
The main goal of any mechanical model is to present a visual illustration of
the concept of creep, relaxation, and viscoelastic behavior occurring simulta
280 Viscoelasticity
neously, and to demonstrate how rheological equations of differential type can
be obtained. The same goal (especially its second part —construction of rheolog
ical models of differential type) can be reached by other methods, for example,
using models based on analogy to electrical properties. In this case, it is possible
to create electrical networks of any complexity consisting of resistors, condens
ers and capacitors. The time dependencies of electrical current and voltage
would also be described by the same differential equations, such as Eq 7.68, and
they can be treated as electrical models of viscoelastic behavior. Such models
can also be very convenient in representing transient behavior of a viscoelastic
medium.
7.8 SUPERPOSITION
The idea of superposition (the discussion in this section must not be confused
with the Boltzmann principle of linear superposition expressed by Eqs 7.31 and
7.32) based on the influence of different factors on viscoelastic properties is
widely used in practice of investigating behavior of real materials. The basic
idea of this approach can be formulated in the following way: the same value of
any viscoelastic function can be obtained either by changing time (frequency) or
physical state of material, the latter governed by change in temperature, con
centration of components, or other parameters. Sometimes, it can be a very un
expected factor; for example, it can be a duration of exposure of a material to
ultraviolet radiation of the Sun (important for predicting longterm behavior of
organic glasses in illuminators of airliners).
The idea of superposition is illustrated in Fig
ure 7.11. Let us have two experimental points for
a creep function measured on the same time
base, t
1
, but at two different temperatures, T
1
and
T
2
. The value of a creep function, ψ
2
, can be ob
tainedintwo ways; first, as showninFigure 7.11,
by direct measurement at temperature T
2
during
time t
1
, and second, at temperature T
1
, but with
time base t
2
. If we know a coefficient a
T
, which
characterizes temperature dependence of a creep
function, we can shift the point (t
1
, ψ
2
) to the po
sition (t
2
, ψ
2
) as shown by the arrow in Figure
7.11.
A. Ya. Malkin 281
Figure 7.11. Superposition of
points of the creep function by
its shift along the time scale 
an illustration.
The temperature coefficient a
T
is
a = log
t
t
T
2
1
[7.69]
or in a general form
a = t a (T)
T
*
T
[7.70]
where t* is a constant and a
T
(T) is a function characterizing temperature de
pendence of viscoelastic properties. A very important supposition is that this
function is the same for any viscoelastic function; it can be proven by the exis
tence of mutual interrelations between different functions characterizing the
viscoelastic behavior of materials.
Now, after shifting the point on the creep function (t
1
, ψ
2
) into a new position
(t
2
, ψ
2
), we have obtained two points onthe isothermal (at T
1
) creep curve and we
can try to reconstruct the creep function curve as shown in Figure 7.11. In fact,
superposing results of measurements of viscoelastic functions on the limited
time (frequency) base or “window” (in Figure 7.11) (it is only one point at t
1
), one
has a possibility to extend the range of experimental determination of this func
tion. It is a very important method because in real experimental practice we
rarely have a chance to make measurements beyond the range of 110
4
s or
10
2
10
3
Hz, except by using the method of superposition. We can extend this
range practically without limit and cover the range of 1215 decimal orders in
time or frequency.
In many real situations, we do not knowthe temperature coefficient, a
T
(T), be
forehand. In order to obtain its value, it is not sufficient to measure only one
point for every temperature. It is necessary to obtain a relationship with some
points having the same values of a viscoelastic function. This approach is illus
trated in Figure 7.12. We have two sections of theG ( ) ′ ω dependencies measured
at two temperatures. In this case, the temperature coefficient is found as a dis
tance between two curves at a height where the values of the modulus at two
temperatures appear to be the same, E
o
′ .
The reduced timescale is calculated as t/a
T
and the reduced frequency scale,
asωa
T
. It is possible to findhundreds examples of applicationof the timetemper
ature superposition in publications devoted to measuring properties of poly
meric materials.
6,7,24
In order to illustrate the strength of this method we shall
282 Viscoelasticity
discuss one conditional (but close to reality) example of superposition of dy
namic modulus measured at rather limited frequency range (Figure 7.13). The
experimental “window” was no wider than 3 decimal orders and therefore only
very limited portions of the full G ( ) ′ ω dependence are known. Superposition
opens this windowand we can nowknowthe values of this dependence in a very
wide range of frequencies.
An empirical approach to timetemperature superposition is possible if all
neighboring portions of the curve have common points. We do not need to know
the a
T
(T) function. However, such treatment of data is not always possible, and
A. Ya. Malkin 283
Figure 7.12. Superposition of two portions of the frequency dependencies of dynamic modulus
measured at two temperatures.
Figure 7.13. Example illustrating superpositionof many portions of frequency dependencies of dy
namic modulus measuredat different temperatures (increasing along the directionof the arrow).
inmany cases, not evenconvenient. That is why it is important to knowthe a
T
(T)
function beforehand.
It was proven experimentally that two possible expressions have general
meaning for the a
T
(T) function. The first of themis the ArrheniusEyringexpo
nential equation, proposed as an analogue to the kinetic equation for the rates
of chemical reactions
a = Ae
T
E/ RT
[7.71]
where A is a frontfactor (coefficient), and E energy of activation of relaxation
processes.
It we choose some temperature T
o
, as a reference point (i.e., if we reduce all ex
perimental data to this selected temperature), then the ArrheniusEyring equa
tion can be written as
a exp
E
R
1
T
1
T
T
o
· −

.
`
,
]
]
]
[7.72]
The second expression for the a
T
function, widely used for timetemperature su
perposition of experimental data in various polymeric materials (it must be em
phasized that polymeric materials and polymerbased compositions are the
main object for application of superpositions of different type), is the socalled
WilliamsLandelFerry (WLF) equation, which can be written as
2527
loga =
c (T T )
c + (T T )
T
1 o
2 o
−
−
[7.73]
where T
o
is the reference temperature, and c
1
and c
2
are constants depending on
the choice of the reference temperature.
If the glass temperature is assumed as a reference temperature the values of
these constants appear rather stable: c
1
is close to 17.4 and c
2
to 51.6. But in fact
it is a rough approximation and it is preferable to use individual values of the
constants which are different for various materials.
As a general rule, it is thought that the WilliamsLandelFerry equationis true
in the temperature range from the glass transition temperature, T
g
, up to
284 Viscoelasticity
T
g
+ 100
o
C. The ArrheniusEyring equation can successfully be used in the
range of temperatures approximately at T > T
g
+ 100
o
C.
If we knowthe formof temperature dependence of a
T
, it allows us not to have to
measure the function a
T
(T) in the whole range of temperatures but to restrict
measurement to some points only in order to verify the constants entering these
equations.
Method of superposition is not limited to reduction of data by means of chang
ing temperature only. The state of a material can be changed for different rea
sons. Variations in content (concentration) of a polymer in a solution is often
usedto change its relaxationproperties. Thenwe canrealize timeconcentration
superposition, and so on.
The method of superposition, used to reduce experimental data along the time
(frequency) scale, is a very powerful possibility to increase the range of observa
tions. At the same time, it must be remembered that the main principle of the
method is based on the assumption that in changing the state of a material its
relaxation spectrum changes in the same manner for all relaxation times, i.e.,
no newrelaxation process appears, no process disappears, and temperature de
pendencies of all relaxation times in a spectrum are the same. The latter as
sumption is confirmed by the fact that the temperature dependence of any
relaxation time is the same as viscosity; and we know that viscosity is the inte
gral representation of all relaxation times (see Eq 7.62). At the same time, it is a
rather strong assumption which may not be fulfilled, especially if superposition
is carried out for initial experimental data obtained in a wide temperature
range. Infact, many cases are knowninwhichthis basic assumptionwas wrong.
One of the most evident examples is a phase transition. If it takes place in the
temperature range under discussion, it definitely leads to radical changes in re
laxation properties. The danger is rather serious for crystallizable polymers be
cause the process of their crystallization takes place in a wide temperature
range.
The second example is that of blockcopolymers:
28
the moveability of blocks of
different types (i.e., possibility to relax) appears indifferent temperature ranges
and reflects freezing of different relaxation modes. It means that different parts
of relaxation spectrum are characterized by different temperature dependen
cies and direct superposition of all portions obtained at different temperatures
is incorrect in principle.
A. Ya. Malkin 285
The third example regards mixtures of different components. In this case, it is
quite obvious that temperature dependencies of relaxation properties of various
components in a mixture, if different, restrict the possibility of superposition of
portions of viscoelastic functions measured at different temperatures.
Examples discussed above show that timetemperature superposition is not a
universal method and has definite limitations. That is why one must be very ac
curate in treating experimental data of a newly investigated material by this
method, especially if far extrapolation, beyond an experimental window, is at
tempted.
7.9 APPLICATIONS OF LINEAR VISCOELASTICITY
There are three mainlines of applications of the theory of linear viscoelasticity.
They are as follows:
• comparison of different materials through constants and functions intro
duced and determined based on the theory
• calculation of the response of a material and predicting its behavior in arbi
trary deformation using results of standard experiments and their theoreti
cal relationships
• comparison of predictions of structure and molecular theories with experi
mental data.
7.9.1 COMPARISON OF MATERIALS BY THEIR VISCOELASTIC PROPERTIES
We can think about two ways of comparison
of different materials. First, it is possible to es
timate the type of a material and to determine
quantitatively such qualitative definitions as,
for example, “solid”, “rigid”, “stiff”, “mild”,
“fluid” and so on. Second, it is possible to com
pare materials of the same type by values of
their constants; e.g., it is possible to distin
guish two rigid materials with different resis
tance to creep. These possibilities are
illustrated below.
As a first example, let us compare typical lin
ear viscoelastic characteristics (frequency de
pendencies of dynamic modulus) of a polymer
286 Viscoelasticity
Figure 7.14. Frequency depend
encies of dynamic modulus of a
polymer melt (A) and a lightly
cured rubber (B), prepared from
this polymer.
melt and a slightly cured rubber prepared fromthe same material (Figure 7.14).
We can see that it is reasonable to select five regions of a frequency dependence
of dynamic modulus for a polymer melt. They are called:
I  flow (or terminal) zone
II  transient viscoelastic region
III  rubbery plateau
IV  transient leathery zone
V  glassy zone.
Certainly, all five parts of the E ( ) ′ ω curve canbe observedfor a single sample by
varying temperature, which results in changing physical (relaxation) states of a
material. Then, one can apply the method of frequencytemperature superposi
tion and construct the generalized E ( ) ′ ω dependence by joining segments of the
full curve and shift along the frequency axis, suchas curve AinFigure 7.14, con
structed for a polymer which can melt at high temperatures (or flowat very low
frequencies).
The first two regions of the complete E ( ) ′ ω dependence for a cured rubber are
absent (curve Bin Figure 7.14), though all other three parts stay practically un
changed in comparison with the melt. It means that, based on the measurement
of the E ( ) ′ ω dependence for an unknown sample, one may find out that it is a lin
ear polymer which can flowand be processed by regular methods or distinguish
it fromrubber able to sustainhigher temperatures and deformations without ir
reversible changes of the shape.
The second example concerns the influ
ence of molecular weight (length of a mo
lecular chain). Figure 7.15 shows that, for
high molecular weight samples, all five re
gions are observed in the E ( ) ′ ω curve. De
creasing molecular weight leads to a shift
of lowfrequency regions (flow and tran
sient viscoelastic zones) of the complete
curve but does not affect the height of the
rubbery plateau and shape and position of
two other regions of the full E ( ) ′ ω depend
ence. However, with a rather low molecu
lar weight member of the same homologous
series, we lose a transient viscoelastic zone
A. Ya. Malkin 287
Figure 7.15. Frequency dependencies
of dynamic modulus for samples of the
same polymer but of different molecu
lar weights. The arrow shows the di
rection of increasing molecular
weight.
(marked as II inFigure 7.14) and rubbery plateau(marked as III inFigure 7.14),
though the flow zone and highfrequency (glassy) part of a curve are present.
It shows that we can distinguish between polymers having different molecular
weights by measuring their viscoelastic properties and comparing the position
of the flow zone and/or the length of a rubbery plateau. It can be used as a rela
tive method of comparison of two polymers by measuring the length of a plateau
or frequencies for any arbitrary level of modulus in a flow zone. If molecular
weight dependence of these factors was known beforehand (for calibrated series
of samples), this approach could have been used as an absolute method of mea
suring molecular weights of polymers.
The third example (Figure 7.16) is a compari
son of a cured rubber and a gel. In both cases,
the first two regions (I and II in Figure 7.14) of
a complete E ( ) ′ ω dependence are absent, such
as for sample B in Figure 7.14. Addition of a
low molecular weight solvent shifts all other
parts of the curve, and in particular, lowers
the height of a rubbery plateau during transi
tion from a cured rubber to a gel.
Figure 7.16 also represents the influence of
increasing density of network crosslinks in a
rubber. This factor is primarily reflected inthe
height of a rubbery plateau and also in the val
ues of modulus in a glassy state.
Examples shown in Figure 7.16 demonstrate
the idea of constructing rubbery materials of different rigidity. Suppose there is
a need for a soft rubbery material for eyesightcorrecting covers. In this case, we
must prepare gels having the required value of rubbery modulus (on the pla
teau). Inanother case, we may need a hard rubbery material for heavy tires, and
again, properties of material are characterized by the rubbery modulus. Regu
lating the content of a plasticizer (low molecular weight solvent) and a harden
ing solid additive, we can reach the necessary combinations of viscoelastic
properties in different frequency ranges needed for the application. For exam
ple, sealants require definite elasticity in the low frequency range and aircraft
tires must be elastic at high frequencies because these products work under
quite different conditions, even though both must be elastic in application.
288 Viscoelasticity
Figure 7.16. Frequency depend
encies of a cured rubber (R) and a
gel (G) prepared from the same
rubber. The influence of higher
density of a network of crosslinks
(curve R’) is also shown.
The last series of examples is, in fact, comparison of materials by their
viscoelastic properties in relations to different areas of their application. In all
these cases (as in many others), the main problem consists in the necessity to
formulate special conditions of application in terms of the theory of
viscoelasticity and to establish the required level of properties. In real life it can
be constants, such as viscosity or modulus, which are integrals (moments) of a
relaxation spectrum of a material, or they can be definite values of viscoelastic
functions at one or some frequencies or moments of time.
For example, it can be very important to know values of the creep function or
the relaxation function on the definite time basis, as already discussed in Chap
ter 4. In this and analogous situations, one does not need to know the theory of
viscoelasticity or to make any calculations, but the application conditions must
be reproducible and a simulating experiment should be performed with all nec
essary standard requirements regarding accuracy and statistics of experimen
tal results. Moreover, in these cases we are not restricted by the limits of
linearity because application conditions do not obey any artificial limitations.
Measurements of viscoelastic properties of a material gives a quantitative
base for reference to different relaxational states: glassy, leathery, rubbery, and
so on. At the same time, it must be remembered that, in fact one does not con
sider the state of matter but its behavior. If some definite frequency was chosen
for measurement of dynamic modulus (for example, standardfrequency of 1 Hz),
the comparison of various materials under these test conditions is straightfor
ward. On the other hand, the same material can look quite different in other fre
quency ranges. A typical rubber can behave like a glass at very high frequency,
as proven by frequencytemperature superposi
tion. For example, in tire application for air
crafts, the high frequency behavior of rubber
must be considered, since a tire must damp vi
brations and can suddenly break if it performs
like a glassy rather than a rubbery material.
In addition to primary classification of materi
als in accordance with their main relaxational
states, some more precise conclusions can be
drawn from measuring the temperature de
pendence of the loss tangent, tanδ. A typical ex
ample of such dependence is shown in Figure
A. Ya. Malkin 289
Figure 7.17. Typical tempera
ture dependence of mechanical
losses in periodic deformations
characterized by loss tangent.
7.17. There are maxima in tanδ and each of them is treated as a relaxational
transition. The most intensive hightemperature maximumis calledthe mainor
αtransitionand identified withglass transitiontemperature. Others, to the left
of the main transition (in the direction of lower temperatures), are marked by
letters of the Greek alphabet, starting fromβ, and are called secondary transi
tions.
It is accepted that eachrelaxational transitionidentified withmaximumof tan
δ corresponds to the condition
ωθ ·1
whereωis the frequency at which temperature dependence of mechanical losses
is measured, and θ is a relaxation time.
During the experiment, the frequency is constant, and by changing tempera
ture, one varies relaxation time. At some temperature, the aboveformulated
conditionis reached and it is a criterionof “transition”. It canbe argued that this
condition corresponds to a maximum of tanδ; in particular, it can be illustrated
by a simple mechanical model of viscoelastic behavior including a single relax
ation time.
One of the popular approaches to treating experimental data of the type shown
in Figure 7.17 relates the tanδ maximum with “freezing” or “defreezing” of mo
lecular movements of different kinds. These data canbe usedto recognize molec
ular process according to their position of “transition” along the temperature
scale. The other side of this approach is the idea that passing through the tem
perature where tanδ maximum is achieved, we change the relaxation state and
spectrum of a material, and therefore the principle of temperature superposi
tion can be applied in the temperature range between two transitions only.
In measuring temperature dependence of tanδ, we also do not need to knowthe
theory of viscoelasticity. It should be treated as a standard “onepoint” (i.e., car
ried out at one frequency) method of characterizing a material. This method is a
bridge for using measurements of viscoelastic properties of a material to under
stand its molecular structure.
290 Viscoelasticity
7.9.2 CALCULATION OF THE RESPONSE
This line of application of the viscoelasticity theory is restricted by the linear
ity requirement, because, at present no nonlinear theory of viscoelasticity (see
the next section of this chapter) is treated as a solid base for a longtermpredic
tion of behavior of real materials or fits the empirical experimental data.
Within the limits of linear viscoelastic behavior, the problem of calculation of
responses to arbitrary loads is completely solved by the Boltzmann superposi
tion principle. The relationships between viscoelastic functions were discussed
above. If we knowa relaxation spectrumof a material, all other calculations are
only a technical problem. The major problemis the accuracy of determination of
a relaxation spectrum based on experimental data.
We shall illustrate real limits of calculation by an example concerning relax
ation and creep of polycarbonate,
29
a typical engineering plastic widely used in
industry. The relaxation curve is approximated by the socalled Kolhrausch
function
30
σ
γ
α
(t) = Ae
 t
where A, γ and α are empirical constants.
The values of the constants in this for
mula were found by a computational pro
cedure and they satisfy the condition:
points calculated with the set of selected
constants according to the Kolhrausch
function lie within the limits of possible
experimental error. These limits were
rather narrow, only about 5%. Then, the
creep function was calculated for three
possible sets of constants (satisfying the
aboveformulated requirement). The re
sults are represented in Figure 7.18,
where the exact creep function is also
drawn (dotted line). A calculated curve
can be rather far from the true creep
function and the error large. It was dem
A. Ya. Malkin 291
Figure 7.18. The results of calculations of
the creep function. The relaxation curve
was approximated by the Kolhrausch
function with three different sets of con
stants (curves 1, 2 and 3). Dotted line is
an exact creep function.
onstrated,
29
that a real relaxation curve can be
approximated in different ways and the
method of approximation strongly influences
the results of calculations. Particularly, the re
laxation curve can be approximated by a sum
of exponent functions (by discrete relaxation
spectrum) andonly 5 members are sufficient to
cover a wide time range of relaxation.
Another example cited fromthe results of the
abovementioned investigations of creep and
relaxation of polycarbonate demonstrates the
effect of nonlinearity. Figure 7.19 shows two
sets of experimental points (open symbols)
measured in creep at different levels of stress
(different initial deformations) and curves cal
culated from a relaxation curve, the latter
measured inthe range of linear viscoelastic be
havior of a material at very low instantaneous
deformation. At initial deformation (1%), the
behavior of a material in creep is linear and
quite well predicted by the theory of linear viscoelasticity from a relaxation
curve. But the creep function becomes strongly nonlinear even at initial defor
mation (2.5%), and the experimental points radically deviate from the calcu
lated curve.
It is also worth noting that nonlinear effects do not appear from the very be
ginning of creep; instead, here is some initial period of creep where points lie
rather close to the calculated curve. It means that linearity in viscoelastic be
havior is limited, not by stress (or deformation) level only but by the time factor,
i.e., a material can be linear in a short range of loading and become nonlinear in
longrange loading. Certainly the duration of this range depends on stress level,
as illustrated by experimental data in Figure 7.20. The limit of linear
viscoelastic behavior (the limit can be determined with some experimental er
ror, too) is a very strong function of stress. Experimental points in Figure 7.20
can be approximated by an expression
t = me
* aσ
292 Viscoelasticity
Fi gure 7. 19. Creep of
polycarbonate at two levels of
stress: initial (instantaneous) de
formation was 1% (1) and 2.5%
(2). Open marks  experimental
points, curves  calculated from a
relaxation curve in a linear
viscoelastic range. 20
o
C.
where mand a are empirical constants (the constant a canbe called a stresssen
sitivity factor, and it equals 0.1 MPa
1
for experimental data in Figure 7.20; this
value depends on material under investigation).
The example shows that the theory of linear viscoelasticity can be applied in
practical calculations but the accuracy of predictions depends on:
• accuracy of initial experimental data
• method used for approximation of experimental points
• confidence of being inside the limits of linearity
• deformation and time ranges for which predictions are made.
All these factors are hard to estimate and this seriously limits the possibilities
of calculation based on the linear theory of viscoelasticity. It therefore should be
applied only when one is sure that the potential problems, listed above, are not
applicable; then the theory of linear viscoelasticity becomes a powerful method
of prediction based on limited experimental data.
A. Ya. Malkin 293
Figure 7.20. Dependence of the time, t*, corresponding to the limit of linear viscoelastic behavior
increep onthe level of stresses at different temperatures. Straight line approximating experimen
tal points is an exponential function.
7.9.3 MOLECULAR THEORIES AND EXPERIMENTAL DATA
Any molecular theory claims to predict the behavior of real materials. One of
the broad areas for predictions is viscoelastic behavior, because relaxation ef
fects are inherent to many materials and primarily to polymeric and colloid sys
tems. That is why results of observations of viscoelastic behavior of different
materials are widely used for comparison with theoretical predictions based on
molecular models of materials.
As a general rule, the theory predicts a relaxation spectrumof a material, and
the mainquestionis, whichtype of experiment is used for comparisonwiththeo
retical predictions? Frequency dependence of dynamic modulus is the most
widelyused method. It is explained by the fact that this dependence canbe mea
sured relatively simply in a very wide range of its argument.
A very important peculiarity of this line of applications of linear
viscoelasticity, which is not important in other cases, is the necessity to have re
liable results of measurements of viscoelastic functions and their application to
very well characterized objects. The last requirement is especially important
but inmany cases, it is quite difficult to have sufficient informationabout a sam
ple needed for formulation and use of a molecular theory, rather than to simply
measure viscoelastic properties of the material. This is a mainadditional limita
tion in comparison of experimental data with molecular theories. Nevertheless,
the reference to viscoelastic properties of a material is widelyused in modern
theoretical speculations.
7.10 NONLINEAR VISCOELASTICITY. INTRODUCTION
Theory of linear viscoelasticity is a rather rare example of a specialized and
closed theoretical approach to describing behavior of a material. It has a rigid
mathematical structure, set of theorems, conclusions, and it can be used for
practical calculations of stressdeformation relationship in arbitrary regimes of
deformations (loading). The theory has two main limitations which were men
tioned above. One of them is the necessity to use initial experimental data for
calculations, which can be determined only in a limited range of an argument
andwithsome experimental error. It canleadto errors incalculations whichcan
be much larger than an error of initial measurement, and as a rule, this error
cannot be estimated at all. It is a natural inherent limitation of the theory.
The second limitationis of a more fundamental nature whichseverely restricts
294 Viscoelasticity
capabilities of the theory, especially in applications for technical purposes. That
is a limitation of linearity. Some possible definitions of the limits of linear
viscoelastic behavior were introduced in discussing fundamental experiments
of viscoelasticity (relaxation, creep, periodic oscillations). This is independence
of viscoelastic functions and constants, appearing in the theory, on the level of
stresses and/or deformations. All these requirements are, in fact, reflections of
the concept of independence of a relaxation spectrum of a material to external
influences.
Many nonlinear effects are observed indeformations of viscoelastic materials.
The main effects were listed and discussed in Chapter 4, and some main types of
nonlinearity, with their inherent causes, formulated. The points below are de
signed to illustrate fundamental reasons for nonlinear phenomena:
• weak (geometrical) nonlinear effects due to possibility of large deformations
of medium
• strong (structural) nonlinear effects caused by changes in relaxation prop
erties (spectrum) of a medium under external influence
• breaking (phase) nonlinear effects, which are results of phase or
relaxational transitions caused by deformations. This physical cause leads
to significant change in relaxation properties of a media, not related to the
properties corresponding to the initial state of a material.
All types of nonlinear effects can be found in deformations of viscoelastic ma
terials. Consequently, in constructing rheological equations of state for
nonlinear viscoelastic materials, we must take into account these levels of
nonlinearity. Certainly, effects of the lower level are always present when
nonlinear effects of higher level are observed. One can expect that strong
nonlinear phenomena related to gradual changes in a relaxation spectrumwill
be accompanied by large deformations, and so on. Moreover, the transition from
one level of nonlinearity to the next, as a rule, is not abrupt, especially if we bear
in mind that the majority of real materials are multicomponent and conditions
of transition are different for components of a material. Certainly the threshold
for transition is different for various materials.
For example: which deformations can be called large? The general answer is:
these which are comparable with 1 (i.e., 100%). But we saw that even at defor
mation of an order of 2.5% (i.e., 0.0025) the behavior of polycarbonate in creep
appears to be nonlinear (Figure 7.19). Moreover, nonlinear effects in deforma
tion of highly filled polymeric
31,32
or colloidal plastic disperse systems
33
(colloidal
A. Ya. Malkin 295
dispersionof naphthenate aluminuminlowmolecularweight solvent)
34
become
quite obvious at deformations of about 0.1%. It is explained by the existence of a
very rigid structure of a solid compound, destroyed at this deformationand lead
ing to change in relaxation spectrum and strong nonlinear effect, such as, for
example, nonNewtonian flow and dependence of dynamic modulus on ampli
tude of deformations.
It has already been mentioned (Chapter 4) that strong and phase nonlinear
phenomena are kinetic effects because changes in a relaxation spectrum and
phase transitions occur in time. These timeeffects superimpose on viscoelastic
timeeffects, and the rheological approach must be combined with a kinetic one
in order to understand what happens to a material and to explain and describe
what we observe in the case of “nonlinear effects”.
The last concluding remarkinthis Introductionto nonlinear viscoelasticity is:
even though there is a complete theory of linear viscoelasticity, no such nonlin
ear theory exists, and maybe cannot exist, but there can be many theories of
nonlinear viscoelastic behavior which seem to explain various nonlinear phe
nomena. At the same time, no theory exists capable of covering all nonlinear
cases because of the diversity of causes of nonlinear effects. For example, it is
convenient to use a flowcurve equationfor a nonNewtonianflowfor appliedcal
culations for transportation of a liquid in pipes, neglecting that a flow curve is
only a consequence of some more general rheological equation of state not
known.
7.10.1 LARGE DEFORMATIONS IN NONLINEAR VISCOELASTICITY
The starting point for developing the concept of viscoelastic behavior in
nonlinear range is the BoltzmannVolterra equation (7.31). It is the most gen
eral representation of viscoelastic response at infinitesimal deformations. The
next stepregards the use of large (finite) deformations discussedinChapter 3.
It is convenient to use two tensors for large deformations: the Cauchy  Green
tensor, C
ij
, and the Finger tensor, C
ij
1
, both are functions of two time moments:
an “initial” moment of time when a point of a body is in its reference state and a
current moment of time, i.e., the moment whendeformations C
ij
andC
ij
1
are mea
sured relative to the reference state. In many cases, the initial (reference) state
is assumed to be isotropic at the point, although it is not always true. For exam
ple, liquid crystalline polymers and reinforced plastics are very important ex
ceptions (or to be more exact, they form another case) because these media are
296 Viscoelasticity
inherently anisotropic materials and rheological description of their properties
and behavior needs special theoretical understanding.
The idea of large deformations andtheir role inrheological behavior of real ma
terials can be illustrated by an example of simple shear. For this purpose let us
write the components of the Cauchy  Green and Finger tensors for
unidimensional simple shear in the plane x
1
 x
2
. Assuming that deformations at
the reference state are absent and that shear at the moment, t, equals γ, we can
write the components of the Cauchy  Green and Finger tensors as follows
C (t) =
0 0
0
0 0 0
and C =
 0
0 0
0 0 0
ij
2
ij
1
2
γ
γ γ
γ γ
γ


















Then, we need to formulate the Boltzmann superposition principle for large
deformations. One of the possible ways to do it is to use a form of rheological
equation of state of rubberlike liquid as proposed by Lodge:
35
σ
ij
0
t
ij
1
(t) = C m(t t )dt
∫
− ′ ′ [7.74]
where m(t  t′) is called the memory function.
It is easy to showthat the memory function is directly related to the relaxation
function by the following equations:
ϕ
ϕ
(t) = m(s)ds; m(t) =
d (t)
dt
t
∞
∫
− [7.75]
These equations show that the memory function is the same as for the linear
viscoelasticity limit and it does not depend on deformation. Using the measure
of large deformation, instead of infinitesimal deformation, we come to some new
results: presence of diagonal members in theC
ij
1
tensor leads to the prediction of
the Weissenberg effect. It appears here as a natural consequence of finite defor
mation, and it is really a second order effect because predicted normal stresses
are proportional to γ
2
. Then, using different combinations of the tensors C
ij
and
C
ij
1
, one can reach correct sign and value of normal stresses (within the limits of
A. Ya. Malkin 297
weak nonlinearity). The statement “using different combinations” shows that
there are various possible paths for generalization of the linear theory of
viscoelasticity and we have no formal ground for unambiguous choice of either
version.
The second power of normal stresses in elastic deformation is a weak nonlin
ear effect resulting from large deformation of a material, which is true for a
viscoelastic solid and liquid as well. The model of rubberlike liquid predicts
some new effects besides normal stresses in shear, important as reflections of
weaknonlinearity. The first one is time dependence of tensile stress observedin
uniaxial extension performed at constant rate of deformation. For linear
viscoelastic liquid at constant rate of extension (and at constant rate of shear),
one expects that stress will grow to the limit of steady flow with constant (New
tonian in shear and Trouton at extension) viscosity, and such level is reached at
t → ∞.
To illustrate what happens to rubberlike liquid, it is convenient to operate
witha singlerelaxationtime model (a relaxationspectrumdegenerates to a sin
gle line relaxation time, θ) because this model gives very spectacular results.
Theory shows that in uniaxial extension of such viscoelastic (or rubberlike) liq
uid, stress dependence on rate of deformation at t → ∞ is
36
σ ε
ηε
εθ εθ
( ) =
3
(1 2 )(1+ )
&
&
& & −
[7.76]
At very low rates of deformation (and the words “very low” mean that the
Weissenberg Number, We = & εθ << 1), we reach the limit of linear viscoelasticity:
the Trouton Law for extensional viscosity. Indeed, at We <<1 ≡ & εθ
λ
σ
ε
η = = 3
&
Increase in the rate of deformation leads to the growth of elongational viscos
ity, as can be derived fromEq 7.76, so the theory predicts increasing extensional
viscosity. However, the most intriguing result can be obtained at We → 0.5.
Eq 7.76 predicts, in this case, an unlimited growth of stress, which is physically
impossible. In fact, it means that at We > 0.5, steady elongational flow becomes
impossible, resulting in rupture of a streamto overcome some critical rate of de
298 Viscoelasticity
formation, determined by the criterion We = 0.5.
37,38
If a (linear) relaxation spectrumis not represented by a single but rather a set
of relaxation times, the expression for stress dependence on rate of deformation
becomes more complex, resulting in preclusion to reach a steady flow regime of
extension at sufficiently high rates of deformation. In the general case, the criti
cal value (equal to 0.5) of the Weissenberg Number must be calculated through
the maximum relaxation time from a spectrum. Moreover, if a relaxation spec
trum of a material is continuous and stretches up to infinity, then the state of
steady uniaxial flow becomes impossible at any low rate of deformation.
The prediction of unlimited growth and thus the rupture of material in uniax
ial extension is very important because the model of rubberlike liquid explains
impossibility of increase in extension rate; for example, in the process of fiber
spinning (very much desired in technological practice) beyond the definite
threshold: a liquid jet would break, which helps to realize even weak nonlinear
ity as a result of large elastic deformations in order to observe this effect.
Now, let us discuss the next interesting and important phenomenon predicted
by the model of viscoelastic (rubberlike) liquid. This is constrained recoil of
sucha liquid after cessationof shear deformation, γ
r
, whichis a functionof time.
Recoverable deformations, γ
r
(t), accompany flowof viscoelastic liquid and canbe
measured after sudden (jumplike) cessation of flow. Recoverable deformations
at t → ∞, socalled ultimate (or “equilibrium”) recoil, γ
∞
, are calculated as
γ
τ ηγ
∞
=
E
=
E
o o
&
[7.77]
where η is viscosity (Newtonian viscosity for linear viscoelastic liquid) and E
0
modulus of elasticity.
It is possible to prove that γ
el
can also be calculated by means of the socalled
Lodge equation:
γ
ψ γ
η
σ σ
σ
el
1 11 22
12
= =
2
& −
[7.78]
A. Ya. Malkin 299
where
ψ
σ σ
γ
1
11 22
2
=
2
−
&
is called coefficient of the first difference of normal stresses (see also p. 74).
Then, one can write a new relationship between material constants of a rub
berlike liquid
ψ
η
1
2
o
=
E
[7.79]
The normal stresses can be expressed as a function of the moments of a relax
ation spectrum because both components in Eq 7.79 are such moments (see Eq
7.62). Then normal stresses appear in the model of rubberlike liquid also as a
secondorder effect, which can be connected with relaxation properties of me
dium.
7.10.2 RELAXATION PROPERTIES DEPENDENT ON DEFORMATION
There is a great variety of nonlinear models which take into account the sec
ond level of nonlinearity, i.e., changing relaxationproperties as a functionof de
formations.
3941
If we go by the way of generalization of Eq 7.74, we can assume
that m(t) is a function not of time only but also of deformation. Because a mem
ory function is a material parameter of matter, its dependence on deformation
must certainly be expressed through invariants of the deformation tensor.
Then, we can write
σ
ij
0
t
ij
1
1 2
= C m[(t t );I ;I ]dt
∫
− ′ ′ [7.80]
where I
1
and I
2
are invariants of the C
ij
1
tensor.
Eq 7.80 is a natural generalization of a model of a rubberlike liquid. However,
practical applications of Eq 7.80 meet with a major difficulty which is common
for nonlinear models of suchtype. It is a problemof determining a memory func
tion with its uncertain dependencies on invariants of the deformation tensor. To
300 Viscoelasticity
overcome this difficulty, Wagner
42
proposed the use of a rather old observation
obtained frominvestigationof deformationof crosslinked rubbers. It was known
that in many practically important cases, a relaxation function (or a relaxation
modulus) at large deformations can be treated as a product of two independent
functions: the first one is a timedependent memory function and the second is a
function of deformation (or in more general case, a function of invariants of the
deformation tensor), i.e., it is possible to separate the dependence of a memory
function on its arguments into two different dependencies based on a limited
number of arguments:
m(t,I ,I ) = m (t)h(I ,I )
1 2 o 1 2
[7.81]
where m
0
(t) is a linearlimit memory function, and h(I
1
, I
2
) is called a damping
function, and the latter reflects the influence of deformation on relaxation prop
erties of material.
It is rather difficult to separate the influence of both invariants on damping
function, h(I
1
,I
2
), because in simple (standard) experiments the two invariants
cannot be changed independently. There are some experimental result related
to large deformations in shear where a single measure of deformations, γ, can be
used. Wagner
42
and Laun
43
demonstrated that a damping function can be ap
proximated by a single exponent
h( ) = e
n
γ
γ
and Soskey and Winter
44
and Larson
45
showed that experimental data can be
satisfactory fitted, if we express a damping function by a power law
h( ) =
1
1+ a
b
γ
γ
Parameters a, b, and n in these expressions are empirical constants.
Other versions of a “nonlinear” memory function are also known and their
generalization, as a function of invariants, can be found in the literature. For
our discussion, the most interesting is, first of all, the existence of the depend
ence of relaxation properties on deformations, and secondly, the rather strong
influence of deformations, regardless of whether they are expressed by an expo
A. Ya. Malkin 301
nential or a power function.
Eq 7.80 is able to predict strong nonlinear phenomena. One can obtain the ex
pression for nonNewtonian viscosity, which is written as
η γ ϕ
γ
γ γ ( ) = (t )
d
d
[ h( )]
0
&
&
& &
∞
∫
′
The final formof the dependence of nonNewtonian viscosity on rate of shear is
determined by the structure of a damping function. Regardless of its exact ex
pression, one may state that the influence of shear appears more strongly on the
longterm side of a spectrum than at shorter relaxation times. In this sense, we
can say that shearing suppresses slow relaxation processes (they do not have
enough time to occur) and this phenomenon increasingly envelopes the part of a
relaxation spectrum (from the longterm side), the higher the rate of deforma
tion is.
Eq 7.81 proposed by Wagner
42
is popular in rheological literature because, in
the form used in Eq 7.80, it can describe many experimental data on nonlinear
relaxation in the range of large deformations. Eq 7.80 also predicts nonqua
dratic dependence of normal stress on shear rate at high rates of deformation,
i.e., it demonstrates that at highrates of deformation, the Weissenberg effect re
flects not only weak but also strong nonlinearity, as well.
ThoughEq 7.80, withseparationof arguments, as inEq 7.81, looks very attrac
tive for describing various rheological phenomena, there are at least two princi
ple contradictions of theoretical predictions based on this approach and
experimental facts. First is the wrong prediction concerning the second differ
ence of normal stresses: according to Eq 7.80, it equals zero, whereas, infact, it is
not; second is the prediction of monotonous growth of normal stresses in tran
sient shearing deformations, whereas, in fact, an overshoot takes place. It
proves that this approach is not universally acceptable.
The next step in understanding and describing nonlinear viscoelastic behav
ior is connected with socalled the KBKZ model of rheological behavior,
46,47
which incorporates both measures of large deformations, the Cauchy  Green,
C
ij
, and Finger, C
ij
1
, tensors. Again, there is some ambiguousness inconstructing
rheological models because both measures of large deformations can enter rheo
logical model as arbitrary form, but they allowone to select combinations which
give the best fit of experimental data.
302 Viscoelasticity
Different forms of the KBKZ equation exist. If we explore the idea of separa
tion of arguments in a memory function, as discussed above, we may come to the
following, relatively simple, expression for the KBKZ model:
σ
ij
0
t
1
ij
2
ij
1
= m(t t )[2
W
I
C (t ) 2
W
I
C (t )]dt
∫
− ′
∂
∂
′ −
∂
∂
′ ′ [7.82]
where W is an elastic potential depending on the invariants of the deformation
tensor, and this elastic potential is essentially the same as used in the theory of
elastic (rubbery) solids (see Chapter 6).
Anelastic energy potential functioninEq 7.82 depends onthe deformationand
therefore on time. The dependence W(I
1
,I
2
) must be determined experimentally
like a damping function in Eq 7.81. There is a vast number of publications de
voted to experimental probing of the predictive strength of this model and deter
mining elastic potential function. Meanwhile, the main advantage of Eq 7.82
over Eq 7.80 is inpredictionof the nonzero second difference of normal stresses.
Freedom in combinating measures of deformations and dependency of elastic
potential on invariants of the deformation tensor provides great possibilities to
use the KBKZ model to fit numerous experimental data and describe various
special effects in behavior of different rheological media.
Both equations (Wagner and KBKZ) explore an idea of the influence of the de
formation on a memory function and thus on a relaxation spectrum of a mate
rial, but using it in a simplified form through separation of inputs of time and
deformation. It allows one to single out the linear limit of relaxation function.
Certainly, it is a particular case, but an important one. Moreover, transition to a
more general (and more complex) model of nonlinear viscoelastic behavior, as a
rule, makes these equations almost unrealistic for practical applications.
There are many other, different approaches to constructing nonlinear rheo
logical equations of state for viscoelastic materials. We do not intend to review
all published theoretical ideas; only fundamental and applicable approaches
were discussed above. It is also worth mentioning that there are numerous at
tempts to take into consideration weak (due to finite deformations) and strong
(due to deformational changes of a relaxation properties) nonlinear phenom
ena, but nonlinear effects of the third level (phase nonlinearity) do not appear
in rheological equations. However, the idea of fracture appears in many cases,
even as a result of a weak nonlinearity as discussed for high rates of extension
A. Ya. Malkin 303
of a rubberlike liquid.
In the conclusion of this section, we shall shortly discuss the applied purposes
of nonlinear theories of viscoelasticity. They are essentially the same as those of
the linear theory, but their applied value is even more pronounced because real
technical applications and technological operations take place at high rates of
deformation and reach large deformations. On the other hand, at present an ap
plied meaning of nonlinear theories is very limited. This is explained by diffi
culties indetermining material functions used intheories and the lowreliability
of their predictions for experimental conditions other than those used to deter
mine material functions.
A large number of investigations were performed to verify the correctness of
prediction of qualitative or (better) quantitative results of simple fundamental
experiments (simple shear, uni and biaxial extension, transient regimes of
shear and extension) by different theories, but seldomly to solve applied techni
cal problems. Only empirical or semitheoretical equations for steady nonlinear
phenomena, such as nonNewtonian flow of liquids or longterm creep of solids
and longterm prediction, including extrapolation, are rather widely used for
solving applied problems.
7.11 CONCLUDING REMARKS
Viscoelasticity is a combination of viscous dissipation and storage of defor
mationenergy. The phenomenonis commonfor practically all materials, though
its importance and potential possibility to observe viscoelastic effects is deter
mined by the ratio of inherent timescale (time of relaxation) and characteristic
time of deformation. Various effects explained by viscoelastic behavior are often
observed and are important for polymeric materials in the form of melts, solu
tions, and colloidal dispersions, solids and reinforced plastics, rubbers and
foams. The mainreasonfor its presence is their wide relaxationspectra, causing
the same order of value as duration of loading (deformation) to always exist.
There are three fundamental experiments which are treated as reflections of
viscoelastic behavior of a matter:
• creep  delayed development of deformations under action of constant force
(or stress)
• relaxation  slow decay of stresses at preserving constant deformation
• periodic oscillations  harmonic changing of stresses or deformations with
relative shift of deformation in relation to stress.
304 Viscoelasticity
These experiments can be carried out in any geometrical configuration of de
formation, primarily at shear or uniaxial extensioncompression.
The experiments allow one to find material characteristics of matter  creep
function, relaxation function, dynamic modulus (and compliance), in
stantaneous modulus, equilibriummodulus and viscosity. If these mate
rial functions do not depend on the level of deformation (and stress), material
has a linear viscoelastic behavior; in the opposite case, material is a
nonlinear viscoelastic body.
For linear viscoelastic materials, the principle of superposition
(Boltzmann principle) is valid. According to the principle, reaction of a material
to all consequent deformations (or stresses) are independent and previous defor
mation does not influence the reaction of the material to the next one. Mathe
matical expressionof this principle is done by a pair of the Volterraequations.
Creep and relaxation functions can be represented as sums (or at a limit as an
integral) of exponential items, and exponents in these expansions are relax
ation and retardation spectra. Calculation of relaxation times in a spec
trum is based on solving integral equations. In principle it can be done
unambiguously if a creep or a relaxation function are known exactly in a full
range of time, fromzero to infinity. Since this is impossible, we are compelled to
use approximate methods in solving integral equations, based on analytical ap
proximation and extrapolation of experimental data. However, accuracy of
these methods is limited by the unavoidable scatter of experimental points and
the ambiguity of their extrapolation beyond the experimental time or frequency
“window”.
Characteristics of a linear viscoelastic behavior of a material are interrelated
to each other by algebraic or integral equations and can be mutually recalcu
lated. That is why the linear theory of viscoelasticity is a closed theory, contain
ing all necessary equations in order to estimate mechanical behavior of a
material in arbitrary stressdeformation situation based on measurements of
any fundamental characteristic of viscoelastic properties of a material.
There is an important method of extending the experimental time (frequency)
“window” based onthe idea of superpositionof experimental data obtained at dif
ferent temperatures or concentration in multicomponent systems at some
other external factors, which should not be confused with the Boltzmann princi
ple of superposition. This method is based on the idea that the same value of any
viscoelastic function can be reached either by changing time (frequency) scale or
A. Ya. Malkin 305
varying a value of an external factor (temperature, concentration and so on).
This experimental method allows us to separate parts of timedependent curves
by their shift along the timescale and thus to obtain a curve over a much wider
range of arguments than can be realized in a direct experiment.
The method of superposition is related to the idea that the dependencies of re
laxation times in a spectrumare the same for all of them, and thus this principle
is not applicable if dependencies of different relaxation times in a spectrum on
an external factor (for example on temperature) are different.
The theory of linear viscoelasticity is used for:
• obtaining objective characteristics of a material, which can be correlated
with their molecular structure and/or content
• verification of conclusions from molecular theories which give grounds for
understanding the molecular structure of a material and intermolecular in
teractions
• calculationof mechanical behavior of a material inarbitrary regimes of their
exploitation (but at rather low levels of stresses).
The theory of linear viscoelasticity works well only withinthe limit of infinites
imal deformations. In increasing deformations, fundamental assumptions of
the theory, and primarily the principle of linear superposition, become inade
quate. The theory requires generalizationbecause numerous effects observed at
large deformations are definitely related to viscoelasticity of a material and are
especially important in real technological practice.
The methods of generalization of the classical theory of linear viscoelasticity
can differ, depending on the proposed and assumed mechanism of nonlinear
ity. Consequently, various theories of nonlinear viscoelasticity were devel
oped. The first step consists of the introduction of a measure of large
deformations instead of infinitesimal ones, which causes ambiguity of predic
tions of nonlinear viscoelastic effects.
The concept of rubberlike liquid (viscous liquid, capable to store large elas
tic or reversible deformations in flow) allows us to explain phenomena related to
weak nonlinear behavior, such as existence of normal stresses in shear flow,
which is an effect of the second (quadratic) order. Moreover, this model predicts
that at sufficiently high rates of uniaxial extension, a steady state flowbecomes
impossible and a stream is broken, due to unlimited increase of stresses.
The concept of rubberlike liquid is not sufficient to understand and to describe
the strong nonlinear effects; for example, nonNewtonian viscous flow of
306 Viscoelasticity
viscoelastic liquids. We need to explore the idea of changing (or modification) of
relaxation properties (or in general sense of changing spectrum) of a matter due
to large deformations as an inherent reason of strong nonlinear effects. It can
be done on the basis of different theoretical or experimental considerations and
then we may arrive at different predictions concerning rheological behavior of a
material.
Efforts of numerous researches are directed primarily to comparison of predic
tions of various existing nonlinear theories withresults of some principle exper
iments in uni or biaxial deformations. This offers the a possibility to find
material functions characterizing nonlinear viscoelastic properties of a mate
rial. However, general theories of viscoelasticity are rarely used for solving con
crete applied problems. Only directly measured nonlinear characteristics are
used for these purposes. For example, nonNewtonian flow curves are used to
solving tube transportation problems, and a creep function measured at high
(nonlinear) range of stresses is used for predicting longterm deformations of
real engineering materials.
7.12 REFERENCES
1. B. Gross in Mathematical Structure of the Theories of Viscoelasticity,
Hermann, Paris, 1953.
2. D. E. Blend in The Theory of Linear Viscoelasticity, Oxford, 1968.
3. R. M. Christensen in Theory of Viscoelasticity. An Introduction, Academic Press,
New York, 1971.
4. N. W. Tschoegl in The Phenomenological Theory of Linear Viscoelasticity.
An Introduction, Springer, Berlin, 1989.
5. A. J. Staverman and R. R. Schwarzl in Die Physik der Hochpolymeren, vol. 4,
Ed. H. A. Stuart, Springer, 1956.
6. J. D. Ferry in Viscoelastic Properties of Polymers, 3rd Ed., Wiley, New York,
1980.
7. A. Tobolsky in Structure and Properties of Polymers,
8. L. Bolzmann, Pogg. Ann. Phys., 7, 624 (1876).
9. A. P. Alexandrov and Yu. S. Lazurkin, Zh. Techn. Phys., 9, 1249 (1939).
10. H. Leaderman in Elastic and Creep Properties of Filamentous Materials and
Other High Polymers, Washington, 1943.
11. T. Alfrey in Mechanical Behavior of High Polymers, New York, 1948.
12. V. Volterra in Theory of Functionals and Integrals and Integrodifferential
Equations, 1931.
13. V. Volterra and J. Pérèz in Théorie générale des functions, GauthierVillars,
Paris, 1936.
14. M. Baumgaertel and H. H. Winter, Rheol. Acta, 28, 511 (1989); 31, 75 (1992).
A. Ya. Malkin 307
15. C. Ester, J. Honerkamp, and J. Weese, Rheol. Acta, 30, 161 (1991).
16. J. Honerkamp and J. Weese, Rheol. Acta, 32, 65 (1993).
17. A. Ya. Malkin, Rheol. Acta, 29, 512 (1990).
18. V. V. Kuznetsov, T. Holz, and A. Ya. Malkin, Rheol. Acta, in press.
19. P. E. Rouse, J. Chem. Phys., 21, 1272 (1953).
20. B. Gross, Quart. Appl. Math., 10, 74 (1952).
21. F. Schawarzl and A. Starerman, J. Appl. Sci. Res., A4, 127 (1953).
22. M. L. Williams and J. D. Ferry, J. Polym. Sci., 11, 169 (1953).
23. K. Ninomiya and J. D. Ferry, J. Colloid. Sci., 14, 36 (1959).
24. S. Glasstone, K. Leidler, and H. Eiring, J. Chem. Phys., 7, 1053 (1939).
25. H. Vogel, Phys. Zs., 22, 645 (1921).
26. G. Tammonn and W. Hesse, Zs. anorg. allgem. Chem., 156, 245 (1926).
27. M. L. Williams, R. F. Landel, and J. D. Ferry, J. Am. Chem. Soc., 77, 3701 (1955).
28. K. K. Lim, P. E. Cohen, and N. W. Tschoegl in Multicomponent Polymer Systems,
Ed. R. F. Gould, ACS, Washington, 1971.
29. A. Ya. Malkin, A. E. Teishev, and M. A. Kutsenko, J. Appl. Polym. Sci., 45, 237 (1992).
30. R. Kohlrausch, Pogg. Ann., 12, 397 (1847).
31. G. V. Vinogradov and A. Ya. Malkin, Inter. J. Polym. Mater., 2, 1 (1972).
32. A. Payne in Reinforcement of Elastomers, Ed. G. Kraus, Interscience, New York,
1965.
33. W. P. Pavlov, G. V. Vinogradov, W. W. Snizyn, and Y. E. Deinega, Rheol. Acta, 1, 470
(1961).
34. A. A. Trapeznikov, Rheol. Acta, 1, 617 (1961).
35. A. S. Lodge in Elastic Liquids, Academic Press, London, 1964.
36. G. V. Vinogradov and A. Ya. Malkin in Rheology of Polymers, Springer, 1980.
37. A. Ya. Malkin and G. V. Vinogradov, Vysokomol. Soed., 27A, 227 (1985).
38. A. Ya. Malkin, J. Rheol., 39 (1995), in press.
39. F. J. Lockett in Nonlinear Viscoelastic Solids, Academic Press, London, 1972.
40. R. I. Tanner in Engineering Rheology, Oxford University Press, 1985.
41. H. A. Barnes, J. F. Hutton, and K. Walters in An Introduction to Rheology,
Elsevier, 1989.
42. M. H. Wagner, Rheol. Acta, 15, 136 (1976); 18, 33 (1979).
43. H. M. Laun, Rheol. Acta, 17, 1 (1978).
44. P. R. Soskey and H. H. Winter, J. Rheol., 28, 625 (1984).
45. R. G. Larson, J. Rheol., 29, 823 (1985).
46. A. Kaye, Note No. 134, College of Aeronautics, Cranford, England, 1962.
47. B. Bernstein, E. A. Kearsby, and L. J. Zapas, J. Res. Nat. Bur. Stand, 68B, 103 (1964).
308 Viscoelasticity
NOMENCLATURE
A Frontfactor (empirical coefficient)
A Intensity of heat dissipation (in viscous flow)
A Surface area (in shear)
A
n
RivlinEricksen tensor of the nth order
a, b Semiaxes of an ellipsis
a, b, c Initial length of edges of a pipe
a
*
, b
*
, c
*
Length of edges of a pipe after deformation
a
ij
Components of the gradient of velocity
a
T
Coefficient of temperature reduction
B Width of a channel
B Transverse size of a plane
B Bulk modulus of compressibility
B
n
WhiteMetzner tensor of the nth order
b Ratio of rotation speeds of two coaxial cylinders
b Width of a rectangular crosssection
C
1
, C
2
Constants in the MooneyRivlin equation
C
ij
Components of the CauchyGreen tensor
C
ij
1
Components of the Finger tensor
C
mf
Dimensionless coefficient of viscous friction
c
1
, c
2
Constants in the WLF equation
D Diameter of a tube
D
i
Invariants of the rate of deformation tensor
D
ij
Components of the rate of deformation tensor
d Linear size (in particular, diameter of a tube)
d
ij
Components of the infinitesimal deformation tensor
d
i
Principal values of the infinitesimal deformation tensor
d
ij
(dev)
Deviatoric part of the d
ij
tensor
E Energy of activation
E Modulus of elasticity (Young modulus)
E
*
Complex (dynamic) modulus
E
’
Real component of dynamic modulus (storage modulus)
E
’’
Imaginary component of dynamic modulus (loss modulus)
E
a
Apparent modulus of elasticity
E
i
Partial moduli
E
i
Invariants of the tensor of large deformations
A. Ya. Malkin 309
E
C
Elastic modulus in compression
E
T
Elastic modulus in extension
E
o
Initial (instantaneous) modulus
E
o
Absolute value of the dynamic modulus (in periodic oscillations)
E
∞
Equilibrium modulus
F Normal force
F
f
Resistance force due to viscous friction
F
i
Force (in various situations)
F
n
Normal force
F
p
Resistance force due to pressure
F
p,1
Component of F
p
related to action of pressure on a surface
F
p,2
Component of F
p
related to action of pressure on a bottom
F
s
Stokes force at movement of a ball through a liquid
F
y
Force at the point of yielding
F
σ
Tangential force
F(θ) Relaxation spectrum
f Deflection
f
max
Maximal deflection
G Shear modulus
G
i
Constants in the theory of rubber elasticity
G
∞
Equilibrium modulus
g Gravitational constant
g
ij
Components of the gradient of relative displacement
H Maximal sagging
H Distance
H Height (in various situations)
H(lnθ) Logarithmic relaxation spectrum
h Gap (constant or current) between two parallel surfaces
h Height of a rectangular crosssection
h
o
Initial distance between two approaching disks
h(t) Damping function (in nonlinear viscoelasticity)
I Axial moment of inertia
I
i
Invariants of the stress tensor
I
*
Complex dynamic compliance
I
’
Real component of dynamic compliance
I
’’
Imaginary component of dynamic compliance
I
i
Partial compliance
I
i
Invariants of stress tensor
I
p
Polar moment of inertia
I
o
Instantaneous compliance
I
x
Moment of inertia relative an xaxis
I
∞
Equilibrium compliance
K, K
n
Geometrical factors
K
c
Geometrical factor for flow along the axis between two coaxial cylinders
310 Nomenclature
K
el
Geometrical factor for an elliptic crosssection
K
(n)
Hydrodynamic factor for a “power” liquid
k
ijkl
Components of the tensor of moduli (for an anisotropic solid)
L Length (of a tube, bar)
L Height of two coaxial cylinders
L(lnλ) Logarithmic retardation spectrum
l Distance from the top of a penetrating body to the bottom of a vessel
l Length (of a sample)
l
o
Initial length of a sample
M Torque
M
y
Torque at the point of yielding (in flexure)
M
z
Torque around the zaxis
m(t) Memory function (in viscoelasticity)
n Exponent of the power law in various rheological equations
n
i
Components of a vector showing the orientation (direction)
P Moving force (in the Stokes problem)
P Resistance force (in the lubrication theory)
p Hydrostatic pressure
p
*
Pressure corresponding to elastictoplastic transition
p
o
Pressure at the edge crosssection of a confusor (or at the outer free surface)
Q Volumetric output (flow rate)
Q
D
Volume output due to drag flow
Q
p
Volume output due to pressure gradient
q Distributed load (in Figure 2.12)
R, R
i
Radius in various situations (of a tube, cylinder, sphere)
R
i
Radius of an inner cylinder
R
h
Radius of a hole (on a cross section of a bar)
R
o
Radius of an outer cylinder
R
o
Initial radius
r Radiusvector, current radius, radial coordinates
r Distance between two points in continuum
r
i
Components of radiusvector
r
o
Radius of the edge crosssection of a confusor
r
o
Radius of a hole
r, z, θ Cylindrical coordinates
S Area (of a surface in extension)
S
p
Static moment of a plastic zone
s Distance between two points
T Total force
T Characteristic time of deformation (flow)
T Duration of an oscillation cycle
T, T
i
Temperature (in various situations)
T
g
Glass temperature
T
o
Reference temperature
A. Ya. Malkin 311
t Current time
t
*
Time characterizing limit of linear viscoelasticity
t
*
Time constant
t
i
Time (in various situations)
t
inh
Characteristic inherent time (of a material)
t
obs
Time of observation
u
i
Components of displacement vector
V Velocity (average velocity)
V
x
, V
z
Components of the velocity vector
V
*
Dimensionless velocity
V
max
Maximal velocity (at the axis of a channel)
V
w
Velocity of a moving wall of a channel
V
i
Velocity of an inner cylinder
V
o
Velocity of an outer cylinder
V
o
Volumeaveraged velocity
v
i
Volume
v
i
Components of the velocity vector
W Work (produced during a cycle of periodic deformations)
W Elastic potential
w
ij
Components of the vorticity tensor
X
i
Components of the vector of body forces
X
H
Displacement of a Hookean spring
X
N
Displacement of a Newtonian damper
X
o
Initial displacement (of a Maxwellian model)
x Parameter
x
o
Initial value of x
x
∞
Equilibrium value of x
x, y, z Cartesian coordinates
x
i
Coordinates of the Cartesian coordinate system
z
*
Distance from a neutral axis to a border of a plastic zone
A, B, C, K, M,
a, k, m, n, p Empirical constants of different equations
De Deborah Number
Re Reynolds Number
Re
R
Reynolds Number related to the radius of a tube
Re
*
, Re
**
, Re
*
Characteristic values of the Reynolds Number
T Taylor Number
We Weissenberg Number
α Angle (in different meanings); constant in various equations
α Coefficient of linear thermal expansion
α Dimensionless eccentricity of two coaxial cylinders
α
o
, α
max
Different values of an angle
312 Nomenclature
β Dimensionless coordinate
β Angle (various meanings)
β* Critical value of an azimuthal angle in formation of vortices
γ Magnitude of shift (in simple shear)
γ Gradient of displacement
γ Empirical constant (in the Kolhrausch function)
γ Deformation in simple shear
γ
z
Recoil strain (recoverable deformation in shear)
γ
∞
Ultimate recoil (“equilibrium” recoverable deformation in shear)
γ = cosα Value used in the solution of the hydrodynamic problem of converging flow
γ = cosα
o
Value used in the solution of the hydrodynamic problem of converging flow
&
γ Rate of deformation (shear rate)
&
γ
w
Rate of deformation (shear rate) at a wall
&
γ
w,N
Rate of deformation (shear rate) at a wall in flow of Newtonian liquid
&
γ
w,VP
Rate of deformation (shear rate) at a wall in flow of viscoplastic medium
∆l
i
Elongation
∆P Pressure drop (pressure difference at the ends of a tube)
∆r Change of a radius
∆V Change of volume
δ, δ
o
Width of thin elements (covers, gaps, and so on)
δ Difference of radii of two coaxial cylinders
δ Outstripping factor (in rolling)
δ Phase (loss) angle
δ
ij
Kronecker delta (the unit tensor)
ε Relative change in the distance between two points
ε Eccentricity of two coaxial cylinders
ε Ratio of the gap width between coaxial cylinders to the radius of an inner
cylinder;
ε Tensile strain
ε
f
Residual deformation
ε
v
Relative change of volume
ε
H
Hencky measure of deformations
ε
ij
Components of the tensor of deformations
ε
o
Instantaneous deformation
ε
o
Amplitude of deformation (in periodic oscillations)
ε
*
Engineering measure of deformation
&
ε Rate of axial deformation (gradient of velocity in extension)
ζ Dimensionless radius
η Shear viscosity (Newtonian, apparent)
η
o
Initial (zero shear) viscosity
η
c
Crossviscosity (in Rivlin’s equation)
η
p
Plastic (Bingham) viscosity
η
s
Viscosity calculated by the Stokes formula
η
o
Viscosity of a liquid droplet
A. Ya. Malkin 313
η
*
Complex dynamic viscosity
η′ Real component of dynamic viscosity (or dynamic viscosity)
η′ ′ Imaginary component of dynamic viscosity
θ Angle (in different meanings); angle coordinate
θ, θ
i
Relaxation time
θ
av
Average relaxation time
θ
ij
Components of the rotations (turns)
λ Draw (extension) ratio
λ Elongational (Trouton) viscosity
λ Characteristic retardation time
λ Dimensionless coefficient of friction
λ, λ
i
Retardation time
λ
R
Dimensionless coefficient of friction calculated through the radius of a tube
µ Poisson ratio
ξ Depth of penetration
ξ Dimensionless ratio of volume output
ρ Density
ρ Radius of curvature of a bar
ρ
l
Density of a liquid
ρ
s
Density of a solid
ρ
o
Density of a liquid droplet
σ Stress; shear stress
σ
E
Normal stress in extension; tensile stress
σ
e
Conventional (engineering) stress
σ
i
Stress at the surface of an inner cylinder
σ
ij
Components of the stress tensor
σ
ij,α
Components of the stress tensor at a plane inclined by an angle α
σ
o
Stress at the surface of an outer cylinder
σ
w
Shear stress at the wall of a channel
σ
y
Yield stress; yield point
σ
yE
Yield stress in simple shear
σ
o
Amplitude of stress (in periodic oscillations)
σ
o
Conventional stress (in uniaxial extension)
σ
1
, σ
2
First and second differences of normal stresses
σ
i
Principle values of the stress tensor
σ
∞
Stored part of stress (in relaxation)
Φ Decay of stress function
Φ(λ) Retardation spectrum (spectrum of retardation times)
ϕ Relaxation function
ϕ Angle of turn
ϕ
max
Maximal angle of turn
ϕ
sp
Relative angle of twisting (turn)
Ψ Delayed deformation function
Ψ
1
, Ψ
2
First and second normal stress coefficients (in Weissenberg effect) according
314 Nomenclature
to recommended Nomenclature
ψ
1
, ψ
2
First and second normal stress coefficients (in Weissenberg effect) according
to Eq 4.11
ψ Creep function
ω Frequency
ω Angular velocity
ω
i
Rate of rotation of the inner cylinder
ω
o
Rate of rotation of the outer cylinder
α λ , Empirical constants
α β γ , , Dimensionless geometrical parameters
A. Ya. Malkin 315
SUBJECT INDEX
Anisotropic
liquids 126
materials 196
Arrhenius  Eyring equation 284
Balance equations 2124, 33
Bar 2426, 53, 212, 218, 226
Barus effect 100
Bending 215, 218
Bingham equation 6869
Bingham viscosity 68, 184
Blazius equation 93
BoltzmannVolterra equations 259
Boundary conditions 132
BuckinghamReiner equation 154
Bulk modulus 189
Carreau equation 66
Casson equation 68
Cauchy rule 13
CauchyGreen tensor 4243, 45, 51, 296
Chemorheology 96
Compliance 189, 248
equilibrium 249
dynamic 252, 269, 271
Constitutive equation 61, 114115, 132, 279
Continuum 7
Converging flow 164169
Colloid solution 1
A. Ya. Malkin 317
Concrete 1
Coneandplate (viscometer) 2930
Couette problem 137
Creep 101103, 248, 292293
Cross equation 66
Cylinder
coaxial 71, 140
thinwalled 26, 29, 227
Deborah Number 80, 120121, 187, 246
Deformation
engineering measure 41, 214
finite (large) 4145, 57
Hencky measure 42
infinitesimal 37, 46, 48, 57
maximal 210
phase transition 105106
principal 45
rate 3940
tensor 36
transient 7476
threedimensional 5657
unrecoverable 119
volumetric 47, 49
Deviator 18, 33
Die swelling (see: Barus effect)
Displacement 35, 40
Dilatancy 96
Drag flow 94, 135, 148
Drag reduction (see: Toms effect)
Draw ratio 98
Draw resonance 89
Dynamic modulus 251252, 268269, 271
Elastic
energy 188
318 Subject Index
potential 109, 114, 188
recovery 103
solids 187, 197
Elasticity 97101, 208
Extensional flow 8990
Finger tensor 43, 45
Flow curve 62, 267
Force 10
Geometrical nonlinearity 101
HagenPoisseuille equation 9192, 149
Hemisphere 28
Hereditary integrals 260
Hertz problem 240
Hooke Law 3, 61, 97
Hooke potential 202
Hookean
behavior 4
solid 3, 189
Hydrostatic pressure 18
Hypothesis of strength 209
Hysteresis loop 95, 256
Instability 7894, 82
Intensity of heat dissipation 109
Invariants 1618, 33
Jet breaking 89
KBKZ equation 302
Karman problem 162
Karman’s strip 104
KelvinVoigt model 278
Kronecker delta 43
A. Ya. Malkin 319
KuhnGuthGamesMark potential 202
Lamé factors 191
Laminar flow 140, 163
Law of equality 13
Liquid 119
Lodge equation 299
Logarithmic spectrum 267
Loss angle 251, 289
Lubricant layer 180
Material objectivity 44
Maxwell model 276
Maxwell liquid 275, 277
Melt fracture 8184
Membrane 28, 234
Memory 41, 261, 297
Microrheology 8
Mises criterion 131, 210
Modulus
dynamic 251252, 268269, 271
equilibrium 272
instantaneous 272
shear 190
storage 252
MooneyRivlin equation 99
MooneyRivlin potential 203
Mullins effect 100, 112
Necking 78, 90, 106
Newton Law 2, 61
Newtonian liquid 86, 122, 139, 173
Newtonian viscosity 62, 122
NewtonStokes Law 24, 123, 171
NonNewtonian liquid 122, 126129
NonNewtonian behavior 3, 63
320 Subject Index
Observation scale 4
Orientational crystallization 106
Orientational dewetting 106
Oscillatory measurements 254
Ostwaldde Waele equation 67
Outstripping factor 178
Paints 1
Periodic oscillations 250
Phase nonlinearity 112
Phenomenological models 2
Plastic collapse 225
Plasticity 70, 208
Plastic behavior 68
Plug flow 70
Point of reference 5
Poisson ratio 4749, 5354, 190, 192
Poisseuille problem 149
Polar coordinates 23
Polymeric materials2
Power law 67, 97, 128, 173
“Power” liquid 145, 152154
Poynting effect 5051, 100
Principle of
coordinate invariance 108
determinism 110
linear superposition 258
local action 110
material objectivity 110
Recoil 299
Reiner liquid 127
Relaxation 249
function 101, 250
spectrum 103, 262, 263, 270
time 80, 262
A. Ya. Malkin 321
Retardation
spectrum 262, 266, 270
time 266
Reynolds Number 79, 83, 91, 93, 162, 170
Rheokinetics 96
Rheology 1,36
Rheological
behavior 93, 124
liquid 7475, 79, 8086, 94
Rheopexy 76, 95
Rigidity 216, 228
Rubberlike behavior 207, 297
Sagging 25
SaintVenant principle 45, 211, 244
SaintVenant problem 211, 244
Scalars 11
Screwless extruder 72
Secondary flows 8489
Sealant 288
Shark skin 82
Shear
modulus 190
normal stress 7274
pure 4953
rate 7576
simple 19, 4953
thickening 62
thinning 62
Solid obstacles 104
Space scale 7
Stokes problem 169
Stress
concentration 32
contact 238
plane 17
322 Subject Index
principal 13, 15, 33
normal 9, 209
shear 10, 142
spherical tensor 12, 19
tensor 124
Structure viscosity 63
Superposition 146149, 258, 281
Surface instability 9091
Taylor instability 84
Taylor Number 8586
Temperature stresses 230
Tensor of moduli 196
Tensors 11, 3738, 4547
Thixotropy 76, 95
Time effects 187
Time scale 7, 282
Toms effect 80, 91
Treska  SaintVenant criterion 130131
Trouton equation 77, 125, 129, 298
Uniaxial
elongation 4749
extension 21, 53, 7678, 123, 192, 212
Unidimensional flow 133
Vectors 11
Velocity 143
VinogradovMalkin equation 67
Virk asymptote 94
Viscoelastic
behavior 76, 103, 245
materials 103, 274
Viscoelasticity 79
Viscoplastic behavior 66, 68, 130
Viscosity
A. Ya. Malkin 323
apparent 64
dynamic 253
elongational 77, 125
Newtonian 64
Trouton 77
zeroshear 64, 174
Volterra equation 305
Vorticity 40, 84
Waving 8990
Weissenberg effect 7074, 297
Weissenberg Number 80, 87
WilliamsLandelFerry equation 284
Yasuda equation 66
Yield point 69
Yield stress 66, 119, 208
Young modulus 98, 190, 192, 195
324 Subject Index
Copyright <Q 1994 by ChemTec Publishing ISBN 1895198097
All rights reserved. No part of this publication may be reproduced, stored or transmitted in any form or by any means without written permission of copyright owner. No responsibilitY is assumed by the Author and the Publisher for any injury or/and damage to persons or properties as a matter of products liabilitY, negligence, use, or operation of any methods, product ideas, or instructions published or suggested in this book.
Printed in Canada ChemTec Publishing 38 Earswick Drive TorontoScarborough Ontario MlE lC6 Canada Canadian Cataloguing in Publication Data
Malkin, Aleksandr Yakovlevich
Rheology fundamentals (Fundamental topics in rheology) Includes bibliographical references and index ISBN 1895198097 1. Rheology .
QC189.5.M35
Title. II. Series
1994
531'.11
C959000003
Content
1 Introduction. Rheology: subject and language 2 Stresses 2.1 General theory 2.2 Law of equality of conjugated shear stresses 2.3 Principal stresses 2.4 Invariants 2.5 Hydrostatic pressure and deviator 2.6 Equilibrium (balance) equations 2.7 Examples 2.7.1 A bar loaded by the constant force 2.7.2 A bar loaded by its own weight 2.7.3 Sagging of a flexible bar or a fiber 2.7.4 Internal pressure in a thinwalled cylinder 2.7.5 Hemispherical membrane under its own weight 2.7.6 Torsion of a thinwalled cylinder 2.7.7 Torsion of a cone over a plate 2.7.8 Stresses in a media moving along a cylinder 2.7.9 Stresses around a circular hole in a sheet 2.8 Concluding remarks 2.9 References 3 Deformation and deformation rate 3.1 Displacements and deformations 3.2 Deformation rate 3.3 Large deformations 3.4 Principal values and invariants of the deformation tensors 3.5 Uniaxial elongation. Poisson ratio 3.6 Simple shear and pure shear 3.7 Examples
1 9 9 13 13 16 18 21 24 24 25 25 26 28 29 29 30 31 32 33 35 35 39 41 45 47 49 53
3.7.1 Uniaxial extension of a bar (beam, fiber) 3.7.2 Shear 3.7.3 Plane deformation (strain) state 3.7.4 Threedimensional deformed state 3.8 Concluding remarks 3.9 References 4 Rheological equations of state 4.1 Main rheological effects 4.1.1 NonNewtonian viscosity 4.1.2 Plastic behavior 4.1.3 Weissenberg effect 4.1.4 Transient deformations in shear (of liquids) 4.1.5 Uniaxial extension 4.1.6 Instabilities and secondary flows 4.1.6.1 Extrudate distortions (melt fracture) 4.1.6.2 Secondary flow 4.1.6.3 Waving in extensional flows 4.1.6.4 Interfacial and surface instability 4.1.6.5 Rheological phenomenon in inertial turbulence (Toms effect) 4.1.7 Thixotropy and rheopexy 4.1.8 Nonlinear elasticity 4.1.9 Viscoelastic behavior 4.1.10 Flow around solid obstacles 4.1.11 Phase transitions induced by deformations 4.2 General principles 4.3 Concluding remarks 4.4 References 5 Rheological viscous fluids 5.1 Definitions 5.2 Newtonian liquid 5.3 NonNewtonian liquids 5.4 Viscoplastic liquids 5.5 Some basic problems 5.5.1 Introduction 5.5.2 Plane unidimensional flow 5.5.3 Flow through straight tubes under pressure
53 54 55 56 57 58 61 61 62 68 70 74 76 78 81 84 89 90 91 95 97 101 104 105 106 111 115 119 119 122 126 130 131 131 133 149
5.5.4 Penetration of a cylinder into a viscous medium 5.5.5 Resistance to rotation of a thin disk in a liquid 5.5.6 Converging (diverging) flows 5.5.7 Movement of a ball through a viscous fluid 5.5.8 Compression of a liquid between two parallel disks 5.5.9 Hydrodynamics of rolling 5.5.10 Flow in lubricant layer 5.6 Concluding remarks 5.7 References 6 Elastic solids 6.1 Definitions 6.2 Hookean elastic material 6.3 Linear anisotropic materials 6.4 Large elastic deformations in solids 6.5 Limits of elasticity 6.6 Some basic problems 6.6.1 General formulation 6.6.2 Uniaxial extension 6.6.3 Bending by a torque 6.6.4 Bending by a transverse force 6.6.5 Torsion of a bar 6.6.6 Temperature stresses 6.6.7 Cylinder under internal pressure 6.6.8 Pressure inside a sphere 6.6.9 Stresses and deformations in membranes 6.6.10 Contact (local) stresses 6.7 Concluding remarks 7 Viscoelasticity 7.1 Introduction 7.2 Definitions 7.2.1 Creep 7.2.2 Relaxation 7.2.3 Periodic oscillations 7.3 Principle of superposition 7.4 Relaxation and retardation spectra 7.4.1 Calculation of continuous spectrum
156 162 164 169 174 178 180 183 185 187 187 189 196 197 208 211 211 212 215 218 226 230 231 233 234 238 241 245 245 248 248 249 250 258 262 264
correlations 7.11 Concluding remarks 7.1 Comparison of materials by their viscoelastic properties 7.6.7.10.10.9. Introduction 7.1 Viscoelastic solid 7.2 Relaxation properties dependent on deformation 7.4.10 Nonlinear viscoelasticity.12 References Nomenclature Subject index 265 268 272 273 274 274 281 286 286 291 294 296 300 304 307 309 317 .6.7 Mechanical models of viscoelastic behavior 7.9.2 Calculation of the response 7.5 Dynamic and relaxation properties .2 Calculating discrete spectrum 7.1 Large deformations in nonlinear viscoelasticity 7.8 Superposition 7.2 Viscoelastic liquid 7.6 Relationships between constants 7.9 Applications of linear viscoelasticity 7.
like any other liquid? • a colloid solution is a liquid. Ya. so which value of viscosity should be considered? • concrete looks quite solid and rigid. but why does it remain on a vertical wall without sagging down. but when subjected to an external force it changes its dimensions (and shape) like liquid. if clay is a solid.A. why does it behave like a liquid? • yogurt in a can is rather thick (its viscosity is high) but after intensive mixing its viscosity decreases. Its origin was related to observation of “strange” or abnormal behavior of many wellknown materials and difficulty in answering some very “simple” questions. it also takes the form of a vessel like any liquid does. Malkin 1 1 INTRODUCTION RHEOLOGY: SUBJECT AND LANGUAGE Rheology as an independent branch of natural sciences emerged more than 60 years ago. which are the reasons for such a behavior? . to increase again when left to rest. appear different when we measure it under varying conditions of flow? • clay looks quite like a solid but everybody knows that it can be shaped. For example: • paint is evidently a liquid because it can be poured into a bottle. but why does viscosity of such a liquid. in contrast to other liquids.
This is not the case with plastics which also change their shape after a force is applied but which continue to change shape. i. now named the Newton . Certainly any natural science pretends to deal with reality and does it by means of phenomenological models. The ideas of a liquid and a solid are also models and their formal (mathematical) representation originated from the classical works of Isaac Newton and Robert Hooke. If this material is solid. Moreover.e. and the appearance of time effect means that something happens to a material in an experimental time scale. His ideas were converted to a more accurate form by Stokes. but then sealant must rapidly “solidify” to prevent its flow out of these spaces. characteristic features of an object. The general feature of all these examples is that they are relevant to many real materials and they all exhibit very complicated superimposition of liquidlike and solidlike properties. Thus.2 Introduction • parts made out of polymeric materials (plastics) look rather solid and hard.. toothpaste or a body paste) must be “liquid” to be smoothly applied and not too “liquid” to remain on the skin. the results of observations depend on a time scale. It means primarily that commonlyused words “liquid” and “solid” are insufficient and we need to introduce a new terminology as a result of understanding particular features of behavior and properties of all the abovementioned and many other materials. Certainly time by itself has no sense. The next common feature of all these newlydiscussed phenomena is the existence of time effects.2 who formulated a general law of liquidlike behavior. rheology is a branch of natural sciences considering real materials with changing structure. Newton1 reflected upon a resistance of liquid to a cylinder rotating in a vessel. When a force is applied to a metallic part it will slightly change its shape and will maintain its new shape for a long time. are all these pastes liquids or not? • sealants widely used in construction must be fluidlike to close (to seal) all spaces (joints) and to fill cavities.Stokes Law: . we need new methods to measure and characterize properties of real materials quantitatively and in adequate terms. time is a reflection of changes in material structure taking place during the period of observation (or experiment). is sealant liquid or not? These examples can easily be extended. Any model is created to reflect not all. but the most important. In general. but they are noticeably different. quite similar to parts made out of metal. why does it “stalk”? • pharmaceutical pastes (for example.
but briefly. but now.1] & where σ is shear stress. is proportional to deformation. Malkin 3 & σ = ηγ [1. is called viscosity (or coefficient of viscosity).Stokes and Hooke. we can say that this law assumes that a force (or resistance) is proportional to a velocity (of movement). However.Stokes and Hooke laws. The exact rigorous meaning of these terms will be discussed below. Hooke3 formulated a similar proposal concerning properties of solids. and γ is rate of deformation. and that is why such materials must be the objects of investigation.2] The coefficient of proportionality is called the Young modulus. in order to be brief. Both models represent properties of many real materials and work well in describing their behavior with considerably high degree of accuracy. the abovecited examples show that a great number of materials used in engineering practice and in everyday life are “strange” and “abnormal” from the point of view of classical concepts of liquid and solid materials. Indeed. ε : σ E = Eε [1.Stokes and Hooke Laws are limiting cases formally lying on the border of rheology. These materials are interesting from both theoretical and applied aspects. The positive statement says that rheology studies materials having properties described by any relationship between force and deformation. The NewtonStokes and Hooke laws appeared to be insufficiently accurate for many in . It is a negative statement (the rule of contraries). and the Hooke Law states that stress. σ E . The coefficient of proportionality. It is important to emphasize again that every model describes (represents) properties of real materials with a different degree of approximation. Rheology relies on the idea that nonNewtonian and nonHookean materials exist in reality. η. This can be treated as the definition of rheology: it is a science dealing with materials having properties not described by models of Newton . the Hooke Law says that the force is proportional to the displacement. named after him. there are numerous other real materials which are not described by the abovementioned Newton . Again the formal meaning of these values will be discussed below. the Newton . Ya.A. E. The law. In this sense. was translated to modern form by Bernoulli.
Then.e. but only assumptions) avoid the problem of the inherent structure of matter. Having in mind the real scale of a physical point. any observer is sure that he sees a body of matter as a homogeneous continuous mass without holes and empty spaces. Characteristic size of a molecule (its crosssection or length of several bonds) is 1 nm. a central physical problem exists in explanation of observed macrofacts on the base of the molecular structure of matter. There are at least two important principle exceptions: • firstly. Both phenomenological laws (i. The number of molecules in such a point is large enough for smoothing and averaging procedures.. This scale must be large enough to distinguish individual molecules or their segments. and throughout its volume all molecularsize fluctuations are averaged. can one neglect molecular structure and treat a body as homogeneous. one would like to understand what happens to a molecule or how intermolecular interactions occur. The obvious way out of these contradictory evidences lies in the idea of the space scale of observation.4 Introduction dustrial materials.Stokes and Hooke laws known to everybody from his schoolyears. nobody is interested in what really happens in a very small volume. which is quite different from a philosophical or geometrical point. In this approach. only when one deals with sizes of the order of 10 nm. the latter is an infinitely small object of zerosize. Almost everybody is convinced that matter consists of molecules and intermolecular empty space. At the same time. • secondly. It means that a characteristic volume is of an order larger than 103 nm3. gave much better approximation of reality than the classical Newton . taken as probable assumptions. This is a real size of a physical “point”. one would come to the macroproperties of a body. The physical “point” contains ≈104 molecules or segments of macromolecule. then going through microvolumes containing numerous molecules and averaging molecular phenomena. if geometrical shapes under consideration have angles and the size at the corner of any an . in some applications we meet with “zero” size. and the only justification for this is the fact that in almost all practical applications. which is why rheology. any material body is heterogeneous. which means that in reality. we think that we have a right to apply methods of mathematical analysis of infinitesimal quantities (which relate to a geometrical point) to a physical medium. The formal extrapolation of physicsbased analysis to infinitely small sizes tacitly avoids the incorrectness of this operation. with its more strict and complex laws and equations.
. we avoid the problem of a geometrical form of a body as a whole and are interested only in its substantial. plastics with mineral filler) where a filler forms a statistical or quite well arranged (in reinforced plastics) structure.e. let us formulate the main problem of rheology. For example. and both adjectives concern a size less than conditionally ≈10 nm. In its origin. Thus when we consider what happens in a body in a point of reference. Rheology studies behavior of various real continuous media. and with the present background we are able to add some additional details to the discussion. a body can have structure and be heterogeneous. Ya. but. In some applications we may not be interested in this structure and continue to treat the medium as homogeneous. That is why analysis of problems of this kind requires special methods. the role of heterogeneity can be important and even a determining factor (for example. applied to a body) and inner reaction (changes of a shape of a body). Pertinent to the above discussion. In other cases. For the continuous media we can extrapolate this approach to a point and examine the relationship between forces at this point and deformation.e.A. in any case. since the . inherent properties. and this is out the realm of physical meaning. i. A very typical example of such heterogeneity is a filled polymeric material (e. Considering all the abovementioned limitations and the physical meaning of terms which have been and will be used. change of a distance between two arbitrary points in a body. we shall consider homogeneous continuous media. In larger scales. a body can be a mixture of some components with steplike transitions between them. it is a relationship between outer action (forces. Extrapolation of calculation results to such zero volumes sometimes leads to infinite values. i. the scale of such heterogeneity has to be much larger than characteristic molecular sizes..g.. What do we mean saying “behavior”? For a body of finite size. the term “rheology” has been related to flowing media. Now we come to a definition of the subject of rheology: it is determination of mechanical properties of continuous media having a different nature. We have already tried to do it from a different perspective. Malkin 5 gle is (formally) equal to zero. for reinforced plastics). averaging inner differences up to much higher scales (for example for many astronomic observations. ascertaining relationships between forces and movements of a matter “in a point of reference”. the sun and our Earth are quite homogeneous and moreover can be treated as “points”).
as Figure 1. Currently. As a result.1. well as having applications to real technological and engineering materials in life.1. the term is used for any real material because sometimes it is very difficult to estimate whether a material is solid or fluid.6 Introduction main root of the word means “to flow” (rheo in Greek). The place of rheology among other natural sciences and applied problems is shown in Figure 1.its place among other sciences considering applied problems. To recapitulate. it seems useful to point out the main ideas of the Introduction insofar as they will allow us to compose a dictionary of Rheology. One can see that rheology is a multidisciplinary science having many points of relationship with fundamental physics and chemistry. Rheology is a science concerned with mechanical properties of various . Rheology . the analytical methods used for both classes of media are very similar.
and intermediate technological and natural products (materials). Rheological behavior of a material depends on time and space scales of observation (experiment). The rheological analysis is based on the use of continuum theories. its mathematical image) and values of constants included in a model — characteristic for a material. The behavior of a material is a relationship between forces and deformations (or changes of shape) and a model gives a mathematical formulation of the relationship. the latter determines the necessity to treat a material as homo. The results of macroscopic description of behavior of real engineering and biological media. temperature distribution or other reasons) but such change occurs gradually. which is a physical object including a sufficient number of molecules in order to neglect the molecular structure of matter and to treat it as continuum. The former is important as a measure of the ratio of the rate of inherent processes in a material to the time of experiment and/or observation.or heterogeneous. these changes are reflected in space dependencies of material properties entering equations of continuum theories which must be formulated separately for any part of material surrounded by the boundary surfaces at which discontinuity takes place • continuity theories include an idea of anisotropy of properties of a material along different directions. and the mathematical analysis of infinitesimal quantities can be used. based on their rheological properties. liquidlike. etc. rheological properties being expressed by the structure of a model (i. Rheological properties of a material can be understood via balance (or conservation) equations (equations of solid state continuum or fluid dynamics). Ya.. and shaping of different materials (plastics and ceramics. are used in numerous applications related to technology of synthesis.). oil industry. emulsions and dispersions in the chemical and food industries. pharmaceuticals. processing. meaning that the following is assumed: • there is no discontinuity in transition from one geometrical point to another. transport. Malkin 7 solidlike. being a method to transit from properties at a point to an observed behavior of an item or a medium as a whole.A.e. Rheological models are related to a point. cosmetics. It accomplishes its goals by means of models representing principle peculiarities of behavior of these materials. their . discontinuities appear only at boundaries • properties of material can change in space (due to the gradient of concentration in multicomponent mixtures.
34. 3. 2. Soc. Section IX of Book II. Papers.. 591 (1911). work of bones). . I. Camb. 19. natural phenomena. 75 (1880). related to classical works by Einstein. Math. such as movement of mud streams and glaciers. One can conclude that the first goal of rheology is a search for stress versus deformation relationships for various technological and engineering materials in order to solve macroscopic problems related to continuum mechanics of these materials. 4. Einstein. 1678. Lecture de Potentia Restitutiva. Principia. R. 1684. 1. REFERENCES 1. The second goal of rheology consists of establishing relationships between rheological properties of a material and its molecular composition content. Newton.4 devoted to viscous properties of suspensions. 289 (1906). understanding laws of molecular movements and intermolecular interactions. 287 (1845). It is an important independent problem related to estimating quality of materials. Trans. and biological problems (dynamics of blood circulation. A. Physik. 8. is sometimes used in this line of thought. G. Phil. The term microrheology. Phys. Ann. and it means that the key interest is devoted not only to movements of physical points but also to what happens inside the point during deformation of a medium.8 Introduction longterm properties. London. Stokes. Hooke.
The specific force at any point of the section is equal to F/S and is a normal stress or tensile stress: σE = F S [2. S. or perhaps to both results simultaneously. it means that we must consider two possibilities: • a dynamic situation in which we need to analyze the result of external forces • a geometric and/or kinematic situation in which it is important how and at which speed distances between different points of a body change.1] .1).is a subject of study by mechanics. Ya. F.the movement of a body in space or its rotation around its center of gravity. The force. An initial projection of stress is very simple and obvious. Malkin 9 2 STRESSES 2. Dynamic situation in any point of a medium is expressed by a physical quantity called stress.A. Let us consider a body (bar). or how local shapes (conditionally drawn inside a body) distort. Only what happens inside a body is of principle subject of our discussion. without any changes to its shape . The first consequence of an external action . The area of its normal section is S (Figure 2. Briefly speaking. and as such it is not relevant for us in this book.1 GENERAL THEORY Any external action applied to a body leads either to a movement of a body in its entirety or to a deformation of its initial shape. acts normal to the surface.
F. i. One may ask: what are the stresses acting on a surface with any orientation in respect to force? The problem can be solved by two vectors: of force. i.e.. a train moving along the rails presses on them at several local zones (where wheels touch a rail).. or σ= T S [2.10 Stresses Figure 2.3).e. n.. We can also imagine a different situation where the force T acts not normal but tangential to the surface as shown in Figure 2. the latter is characterized by normal. we eventually come to the limit of the ratio ∆F ∆S at ∆S → 0 and this limit is a normal stress at the marked point: σ E = lim( ∆F ∆S → 0 ∆S) = dF dS This formula shows clearly that the stress is related to a point and can change from point to point. If the area of the surface is S. be a function of coordinates. and orientation of a surface. . to find a relative (specific) force acting on the area ∆F ∆S. For example.2. The force at a free surface may not be constant but distributed. stress is a force related to the unitary surface area.e.2] These simple and obvious relations must be generalized to an arbitrary orientation of an applied force. to surface (Figure 2. Figure 2. a force is distributed along a rail and as a result a very complex pattern of stresses acting in the body of a rail appears.2. Shear of matter. A bar loaded by a normal force. i. If we decrease the surface area.1. then the tangential or shear stress is equal to T/S. ∆S. we can mark a small area. In this case.
There are physical characteristics which must be defined not only by their size but also by a direction of their action. It means that for complete characterization of a stress we need to know two vectors: of a force and a normal to a surface to which this vector is applied. Such objects are called scalars. Malkin 11 We know that there are physical concepts which can be presented by one quantity only. The physical objects which are determined in such a manner are called tensors. 3) must be divided by the area which gives components of a stress tensor. for example. We deal with stresses. F3) Then the nine values can be constructed: three projections of F on surfaces determined by any of the three coordinate vectors. but three quantities . For their complete characterization it is necessary to know not only the value of a force acting at a point (this force is a vector by itself) but also its orientation in respect to a surface to which this force is applied (and orientation is also presented by a vector). n3) F = F(F1. σij. Such physical objects are called vectors. n.projections of velocity along three coordinate axes . 2.A. and orientation of a surlocity. F. and not one face. Any vector can be represented by its three projections along the orthogonal coordinate axes: n = n(n1. As the area of a surface is not essential. such as veFigure 2. all values of Fi (i = 1. The result is written in the form of a table (matrix) . F2.3. Ya.are necessary to determine velocity. such as density of a matter. Force vector. and that is why stress is a tensor. n2. where the first index shows the orientation of a force and the second index designates the orientation of a surface. for example.
In order to emphasize that this set of parameters presents a single physical object . Definition of the compostress distribution) appears to be very comnents of the stress tensor. There are some fundamental facts concerning the stress tensor (and any other tensors as well) and they will be discussed below. The table within the bars is the set (or a list) of all components (projections) of a force vector applied on differently oriented planes at an arbitrary point inside a body. quite equivalent to the initial definition of the normal stress in Eq 2.2. But the stress field (or Figure 2.1. . It depends on configuration of outer forces applied to a body. One can easily see that components with the same numbers in the index are normal stresses. Some other examples illustrating stress distributions will be discussed at the end of this Chapter. The directions of the normals are indicated by the second indices. the second column gives the same for the x2axis and the third to x3axis. the force field is homogeneous for the situation shown in Figure 2.4. and all values with different numbers in the index are shear stresses. For example.12 Stresses σ 11 σ ij = σ 21 σ 31 σ 12 σ 22 σ 32 σ 13 σ 23 σ 33 where the first column represents components of a force (of a vector of a force) applied at the plane normal to the x1axis. for example in a liquid flowing inside a channel or in a case of roof covered with snow. as in Eq 2.stress tensor .1 and in this case a stress tensor is constant (inside a body). plicated in many other cases.4.it is usual to put them between the bars. All components of the stress tensor are determined at a point and can be constant or variable in space (inside a medium). The picture which shows all components of a stress tensor acting at a point is drawn in Figure 2.
σ 23 = σ 32 These equalities are known as the Cauchy rule:1 σ ij = σ ji The result means that only three independent shear components of the stress tensor exist. The idea of principal stresses (maximal and minimal) appears as a consequence of the dependence of stresses on orientation of a surface.4.5. three normal (σ 11 . is calculated as in Eq 2.and σ 23 = σ 32 ).A. σ E . Ya.and σ 33 ) and three shear stresses (σ 12 = σ 21 .2 LAW OF EQUALITY OF CONJUGATED SHEAR STRESSES Let us consider a plane section of a unit cube in Figure 2. Let us illustrate it by two simple examples generated from Figures 2. The rotational equilibrium condition about the central point of the square gives the equality σ 12 = σ 21 The same is true for any other pair of shear stresses: σ 13 = σ 31 . Plane stress state. and the stress state Figure 2. σ 22 . σ 13 = σ 31 .1 and 2. Malkin 13 2. 2. at a point is completely defined by six independent values. The section is shown in Figure 2.1.5. The normal stress. Decomposition of the normal force at the arbitrary oriented surface.2. The following question .3 PRINCIPAL STRESSES Figure 2.6.
at α = 0 at α = 45 o at α = 90 o σ E. In this case we can write the following equations for σ E. σ = σ E 2 = max σ E = 0 and σ = 0 (plane free of stresses).6)? It is easily seen that the vector F can be decomposed into normal Fn and tangential Fσ components to the surface aa. α = 2σcosα sinα = σsin2α σ α = σ(cos 2α − sin 2α ) = σcos 2α Again there are some peculiar orientations: Figure 2.7 allows one to analyze the situation similar to the picture shown in Figure 2. α = 0 and σ α = σ (equivalence at α = 0 and α = 90 o is the consequence of the Cauchy rule). α . Figure 2. α = 0 and σ α = σ σ E.14 Stresses needs to be answered: if the force equals F as before. Projections of the shear stress at an arbitrary oriented surface. there are normal and shear stresses at this surface. stresses (forces divided by the surface area) depend on α and are equal to σ E . so σ is a shear stress. α = σ = max and σ α = 0 σ E. α and σ α : σ E. meaning that normal. σ α .2. The area of this surface is S/sinα. and shear..α = σα = Fn F sin 2 α sin α = = σ sin 2 α S S Fσ F sin α cos α σ sin α = = sin 2α S S 2 There are some interesting and peculiar orientations in a body: at α = 90o at α = 45 o at α = 0 σ E = max and σ = 0 (the later is evident from Figure 2. σ E. what are the stresses acting at the surface inclined to the vector F at the angle α (Figure 2. i.e. .1).7. Let the area of both sides of a cube be equal to a unit.
Examples of such situations have been shown above for the cases drawn in Figures 2. i. Moreover. that is why it is important to know the value of maximal normal stress acting in a material. The abovediscussed examples are only illustrations of a general idea that all components of a stress tensor depend on orientation of a surface. at which normal stresses are extremal and shear stresses are absent. it breaks as a result of an action of normal stresses.. . whereas shear stresses are practically negligible in this case. and this maximal stress is the principal stress. it is very difficult to compress a liquid (compression is an action equivalent to application of negative normal stresses) but it is very easy to shear a liquid (to move one layer relative to another like cards in a pile). It is impossible to compare stress states at different points of a body or in different bodies if only operating with six independent components of the stress tensor acting along different directions. The main interest and the result of all these calculations and discussions are connected with the existence of such direction in a body where stresses are extremal. The last result is very important because various media resist application of extension (normal force) or shear (tangential force) in different manner. Another case: when a thin film is stretched (it can be a cover of a balloon stretched by the inner gas pressure). For example. Indeed. Malkin 15 The discussion shows that. there are always directions where either normal or shear stresses are maximal. Theoretical analysis shows that for any arbitrary stress tensor it is possible to find three orthogonal. The existence of principal stresses is a general law for any stress tensor. Ya. one can expect that some materials are ruptured by an action of a normal stress if it reaches a critical level. σ ij = 0. perpendicular to each other. The concept of principal stresses allows one to find a minimal number of parameters which completely characterize the stress state at any point.1) or only shear (Figure 2.2) stresses.6 and 2. normal stressesσ ii = max at these directions at which shear stresses are absent. in fact. both normal and shear stresses can exist irrespective of simple pictures with only normal (Figure 2.7. directions. It is a result of projecting a vector along different directions: the size of a projection depends on orientation of the axes in space. There are general rules and equations for calculating components of the stress tensor at any direction.e. at any arbitrary orientation (or direction) in a body.A. α and σ α . These normal stresses are called principal stresses. For example. generalizing equations written above for σ E. It is much easier to do so dealing with only three normal stresses. for which one wants to calculate them.
rupture of solid bodies.4] and principal stresses are three roots of this equation designated as σ 1 . probability for a “quasiliquid” to stick to a vertical wall and stay motionless in spite of action of gravitational force.) can be considered as a consequence of an action of principal stresses only. This leads to the conclusion that I1. Principal stresses represent stress state in a body (at a given point). . and every different stress state is equivalent if principal stresses are the same for all of them. and they are expressed through values of I1. In other words. and I3 are also invariant in respect to the choice of directions of orientation and that is why they are usually called invariants of a stress tensor at a point. and I3 is a cubic invariant.7] As the roots of Eq 2. I1 is a linear. they are invariant in respect to the choice of orientation. on the other. σ 2 .16 Stresses 2.and σ 3 do not depend on orientation of axes of a unit cube (at a point) in space. These coefficients are constructed by means of all components of stress tensor for arbitrary orthogonal orientations in space as: I1 = σ 11 + σ 22 + σ 33 2 2 I 2 = σ 11σ 22 + σ 11σ 33 + σ 22σ 33 − (σ 12 + σ 2 + σ 13 ) 23 2 2 2 I3 = σ 11σ 22σ 33 + 2σ 12σ 23 σ 13 − (σ 11σ 23 + σ 22σ 13 + σ 33 σ 12 ) [2. It is clear that the roots are expressed through coefficients of Eq 2. regardless of any possible set of normal and shear stresses at any arbitrary orientation of this point.4. in particular. Then the question is: how to calculate principal stresses if all components of the stress tensor are known for some arbitrary coordinate system? Theory of tensors gives an answer to this question in the form of a cubic algebraic equation: σ 3 − I 1 σ 2 + I 2 σ − I3 = 0 [2.4.4 INVARIANTS If we can calculate principal stresses. and I3.5] [2. on one hand.6] [2. I2. etc. According to its structure (the power of components). I1. I2 is a quadratic. slow movement and transition to spurt for snow. σ 2 . This means. the σ 1 . it means that we can represent the stress state of matter by three independent values. sand or mud on slopes. I2. σ 3 . I2. that various physical phenomena taking place under stress (for example. and I3.
is also invariant in respect to the orientation of axes in space.2 = 11 ± 2 2 2 2 + σ 12 1 2 Typical examples of thin (or twodimensional) elements are various balloons. Various elegant or cumbersome structures of invariants are possible to be built but it is important to know that three and only three independent values of such kind do exist. σ 3 . I2. In the plane stress state.8] In this case. is zero and two others. storage of elastic energy or dissipation (transition to heat) of work of external forces. It means that neither any stress by itself nor its arbitrary combination but only invariants determine a possibility of occurrence of various physical effects such as. Malkin 17 Certainly any combination of the invariants. In many practical problems. which are values independent of a coordinate system. they might not vary appreciably over the small distance (thickness of the item).A. σ 1 and σ 2 . “Thin” means that the size in direction normal to the surface is much smaller than other two dimensions. govern physical phenomena occurring due to application stresses. Stresses in planes parallel to the free surfaces can be assumed to be absent in comparison with stresses at two other oriented planes. and I3. one principal stress. The very typical example of it are thinwalled items with stressfree outer surfaces. for example. . Ya. phase transitions. are the roots of a quadratic (but not cubic) algebraic equation: σ + σ 22 σ 11 − σ 22 σ 1. There is a fundamental principle saying that physical effects must be independent of choice of a coordinate system and that is why invariants. I1. Invariants are characteristics of the physical state of a matter. all the components containing the index “3" vanish and the full stress tensor looks like this: σ 11 σ ij = σ 21 0 σ 12 σ 22 0 0 0 0 [2. we deal a with twodimensional or sonamed plane stress state. This can be proven by a pure geometrical argument: because stresses are zero on both faces.
these cases were mentioned at the very beginning of this chapter.6 and 2. There are two particularly simple cases of the plane stress state. which are simple (or unidimensional) tension and simple shear. And for all these articles and many others. p (Figure 2. and their tensorial nature is illustrated by the abovediscussed Figures 2. In fact.8. barrels and tanks. all principal stresses are the same and equal to p: σ1 = σ 2 = σ3 = − p .e. singling out the components connected to action of the normal stresses. Alldirectional compression (hydrostatic pressure). Let us consider the situation of alldirection compression of a body under pressure. while shear stresses distort its form (shape). The main feature of hydrostatic pressure is the absence of shear stresses.18 Stresses membranes and covers.5 HYDROSTATIC PRESSURE AND DEVIATOR Figure 2. all components of the matrix except normal are equal to zero and the stress tensor for this case looks like this: [2.9] p 0 0 0 p 0 σ ij = 0 0 p i. It seems quite obvious that only normal stresses can change the volume of a body. 2. For this reason it appears to be reasonable to divide a stress tensor into two components.7 and rules of a transformation of stress components with rotation of coordinate axes.8). hence. This case is called hydrostatic pressure. we can use the analysis of the twodimensional (or plane) stress state. and so on..
σ ii = − p. For plane shear stress state. The hydrostatic pressure (or simply . hydrostatic . For the hydrostatic pressure σ ij = − pδ ij .10 is considered as a general definition of pressure. whenσ 12 = σ 21 .10.11] The same conclusion is correct for all other shear components of the stress tensor. and σ 33 are not equal to each other..A. Eq 2. Malkin 19 The expression 2. I1 = 0. σ 22 . There is one intriguing question: whether the value I1/3 calculated according to Eq 2. Then p 0 0 0 0 1 0 p 0= p 1 0 0 σ ij = 0 0 1 0 0 p The remainder in bars is called the unit tensor or Kronecker Symbol. i.e. σ ij = 0 if i ≠ j For this stress tensor shear.8. the principal stresses are equal to σ1 = σ E .9 can be written in a short form if to use some evident rules for operation with tensors which allow a constant to be taken away from bars. and the stress tensor. and called pressure. Ya.9. has the same physical meaning as pressure used in any thermodynamic relationship? Certainly. It means that for this situation called simple shear.pressure) is evidently expressed as p= − I σ 11 + σ 22 + σ 33 =− 1 3 3 [2. i. σ 2 = σ E .e. σ3 = 0 [2. is called the spherical stress tensor.10] The last definition is taken to be true for any stress state. even when σ 11 . and it explains the term “hydrostatic” used for the situation shown in Figure 2. δ ij . but this idea of arbitrary stress state needs a separate proof. the stresses are absent at any direction in space. it is true for hydrostatic pressure. and Eq 2.
it follows that p = . all shear stresses remain untouched and each diagonal member of the tensor becomes equal to σ ii − p. Now we can write down a general expression for any stress tensor with a separated hydrostatic component. This part of the stress tensor (complete tensor minus hydrostatic component) is called deviator or deviatoric part of the stress tensor. In this approach.20 Stresses pressure does not exist.12 as a sum of hydrostatic pressure and remainder. and is it equivalent to hydrostatic pressure? Stress tensor for uniaxial extension is written as σ 0 0 0 0 0 σ ij = 0 0 0 [2. σ 22 = 0 and σ 33 = 0 From Eq 2. where all other forces except normal force. There is no reason for the appearance of other stresses except for σ 11 . Now let us present the stress tensor 2. In the case under discussion. where this “remainder” is deviator or simply a difference between full stress tensor and hydrostatic pressure. But is it all.10.12 shows that σ 11 = σ E . the matrix 2. Let us separate this tensor into hydrostatic and deviatoric parts. Then the stress tensor for uniaxial extension can be written as: . and that is why all components in the matrix 2. are absent.1.12] It reflects the situation in Figure 2.σ E /3. The idea about splitting a stress tensor into spherical and deviatoric parts is well illustrated by the example of uniaxial extension. except for σ 11 = σ E . It is thought that this part of the tensor is responsible for changes of shapes of a body (certainly at a point).12 are zeros. It proves that indeed shear stresses do not influence the volume of a body but are able to change its shape only. F. Surely it is extension and we have a right to expect that it leads to a volume change of a body.
6 EQUILIBRIUM (BALANCE) EQUATIONS The distribution of stresses throughout a body is described by equilibrium (or balance) equations introduced by Navier. is equal to the sum of components of both addenda with the same indices. 2. Ya.σE 3 0 0 2 0 0 σE 0 = pδ ij + 0 1 0 3 0 1 0 1 . The idea of the analysis consists of a projec .6.σ E 3 Any component of the full stress tensor.2 Poisson.4 In essence they are one form of Newton’s Second Law written for a continuum because they state that the sum of all forces at a point is equal to the product of mass (of this point) times acceleration. A “point” in the theoretical analysis is an elementary (infinitesimal) space with sides oriented along the orthogonal coordinate axes (in Figure 2. it means that we can find such directions in a body where the shear stress exists (opposite to hydrostatic pressure where the shear stresses are absent in principle) as mentioned in discussion of Figure 2. In particular.9 this space is a cube in the Cartesian coordinates).σij. This interpretation of the uniaxial extension explains that in fact onedimensional tension creates not only negative pressure (“negative” means that stresses are oriented from unit areas inside a body) but also different normal stresses acting along all directions. This is a physical reason why in the uniaxial tension all dimensions of a body change: a size increases along the direction of extension but decreases in perpendicular (lateral) directions.A.3 and Cauchy. for example: σ 11 = − p + 2 1 2 1 1 1 σ E = σ E + σ E = σ E and σ 22 = − p − σ E = σ E − σ E = 0 3 3 3 3 3 3 One can see that the uniaxial extension is not equivalent to hydrostatic pressure (the sign is not essential in this discussion) as the former leads to appearance of a deviatoric component of the stress tensor. Malkin 21 2 σ 3 E σ ij = − pδ ij + 0 0 0 1 .
it is reasonable to treat problems restricted to static equilibrium. For most rheological applications. Writing the sum of projections of all stress components parallel to x2axis and dividing them by (dx1dx2dx3). a(a1. Stress difference at parallel surfaces along the infinitesimal distance. for example. in [2. and hence a = 0. in many cases (but not always) vector X equals zero. X2. Besides. Let us consider a change of forces at infinitesimal distance along an axis. and on the parallel rig h t h a n d fa ce i t e q u a l s t o σ′ 22 = σ 22 + (∂σ 22 ∂x 2 )dx 2 and the sum of projections of forces is w h e re (∂σ 22 ∂x 2 )dx 2 (dx1dx3 ). a3) is a vector of acceleration and ρ is the density. (dx1dx3) is the surface area of the face. Figure 2.9) equals to σ22.9. we can think that (for example) a force on the lefthand face of the cube (Figure 2. The existence of a body force is important. a2. X3) is a vector of a body force per unit volume (dx1dx2dx3). For all three coordinate axes. If there is no special situation with jumps or breaks in force. we come to equilibrium (or balance equations or equations of moment conservation).22 Stresses tion of all outer forces on faces of the cube along three coordinate axes. this approach gives the system of equations: ∂σ 11 ∂σ 12 ∂σ 13 + + + X 1 = ρa 1 ∂x 1 ∂x 2 ∂x 3 ∂σ 12 ∂σ 22 ∂σ 23 + + + X 2 = ρa 2 ∂x 1 ∂x 2 ∂x 3 ∂σ 13 ∂σ 23 ∂σ 33 + + + X 3 = ρa 3 ∂x 1 ∂x 2 ∂x 3 where X(X1.13] .
13. Components of the stress tensor in cylindrical polar coordinates. flowing of glaciers and so on. Eq 2. z. T h e ch o i ce o f coordinates is only a question of convenience in solving a concrete boundary problem.13a] . the most convenient coordinate system in this case is cylindrical polar coordinates Figure 2.A. on the shape and type of symmetry of a geometrical space of interest for the application. The choice of the coordinate system depends. z. Malkin 23 situations where the movement occurs because of the action of gravity: in sagging paints or sealants from vertical or inclined surfaces. Ya.10 represent equilibrium in respect to r. with r. Components of the stress tensor in these coordinates are shown in Figure 2. it allows us to simplify the system. and θ directions and can be written as: [2. if we deal with problems related to round shells or tubes with one axis of symmetry. and θaxes.10. For example.10. The static balance equations (at a = 0) for the point (or infinitesimal volume element) shown in Figure 2. generally speaking. If we can omit two last members in the balance equations. and in this case we can write it as follows: ∂σ 11 ∂σ 12 ∂σ 13 + + =0 ∂x 1 ∂x 2 ∂x 3 ∂σ 12 ∂σ 22 ∂σ 23 + + =0 ∂x 1 ∂x 2 ∂x 3 ∂σ 13 ∂σ 23 ∂σ 33 + + =0 ∂x 1 ∂x 2 ∂x 3 Equilibrium can be considered in respect to different coordinate systems but not restricted to a Cartesia n sy st e m .
14] [2. XΘ. when one suspends a weight on a string or pulls a car from mud with a rope. .all cases deal with a material under the action of uniaxial extension. Besides. 2. appears when a material or a part is compressed in one direction. Some applied problems are symmetrical about the zaxis. so that all terms containing ∂ ∂θterms become zero and the shear stress σ rΘ as well.7 EXAMPLES [2. Xz) is a vector of a body force and its projections along the cylindrical coordinates.15] It seems interesting and useful to present and discuss typical examples of stress distributions in a body for some model situations. in some cases.7. This allows us to continue simplification of the balance equations.1) This is a very popular scheme of loading. as in pile loading or in building foundation. for example. or stretches a filament in the technology of fiber spinning . 2. A similar scheme of loading. which in this case reduce to dσ rr σ rr − σ ΘΘ + + Xr = 0 dr r and all shear components of the stress tensor are absent.24 Stresses ∂σ rr ∂σ rz ∂σ rθ σ rr − σ θθ + + + + Xr = 0 r∂θ r ∂r ∂z ∂σ rθ ∂σ θθ ∂σ θz 2σ rθ + + + + Xθ = 0 r∂θ r ∂r ∂z ∂σ zz ∂σ θz ∂σ rz ∂σ zz + + + + Xz = 0 r∂θ r ∂r ∂z where X(Xr. but with the opposite sign. the cylindrical bodies can be very long and variations of stresses along the axis of symmetry are absent (or can be taken as negligibly small).1 A BAR LOADED BY THE CONSTANT FORCE (FIGURE 2. for example.
16] Figure 2. A long bar loaded by its own weight.1. after leaving a nozzle. or a plastic liquidlike stream. the distribution of forces at the end becomes unessential for stress distribution throughout the bar and normal stresses are calculated by the very simple and obvious relation 2. According to the equilibrium condition σ(x) = ρx [2. breaks by its own weight at some distance from the nozzle. The reasonable supposition says that the height of flexure is much lower than the length of the bar. the stress will exceed any acceptable limit and break the bar. It means that if the bar is very long.12 2. all components of the stress tensor for different directions can be found. The maximal normal stress is equal to σL. fibers and so on) is a rather typical situation in many practical applications.12. .11) It can be found in some engineering constructions where parts are suspended at their upper end. expressed as a force divided by the length. push of the wind. we deal with distributed load.7. q. Malkin 25 The stress distribution near the buttend of a bar depends on the manner of counteracting the force. (in Figure 2.2 A BAR STRETCHED BY ITS OWN WEIGHT (FIGURE 2.11. Ya. By the abovediscussed method. A sagging bar (fibre).A.7. The force provoking bar sagging can be caused not only by the own weight of the bar but also by various outer factors (lying snow.3 SAGGING OF A FLEXIBLE BAR OR A FIBER (FIGURE 2. L. Far enough from the buttend (typically at a distance larger than the characteristic transversal size of a bar). Sagging of flexible engineering elements (bars. where L is the length of the bar. The extensional (normal) stress along the bar appears as a result of stretching by its own weight. and so on). In all these cases. or a span between supports.12) Figure 2. Let a long bar (or a fiber) be suspended by its end. 2.
and vice versa.13. This situation is of general meaning for all vessels working under internal pressure.7.qx = 0 2 or y= qx 2 2F The last formula shows that the shape of the loaded bar is parabolic. boilers. It is easy to find the maximal sagging. 2. we have: x Fy . H: H= qL2 8F [2.13) Figure 2. A thinwalled tube (cylinder) under internal pressure. . The normal stress in the bar is evidently equal to F divided by the crosssection. such as chemical rectors.17 allows us to find the necessary tension if we set acceptable flexure.17] Eq 2. plastic films stretched during technological procedure of their shaping.4 INTERNAL PRESSURE IN A THINWALLED CYLINDER (FIGURE 2. According to the equilibrium condition (the sum of torques around the point of suspension is equal to zero). tubes in tires. and different types of balloons. and so on.26 Stresses only a half of the bar is shown).
The situation changes if we assume that such a Figure 2. It is evident that σ r = 0at the outer surface and σ r = p at the inner surface of the cylinder. Malkin 27 Let us try to calculate stresses in the wall of a cylinder loaded by internal pressure. Are other components of the stress tensor essential? We can estimate the σ rr component (or simply σ r ).14. Stresses in a vessel must be closed by a lid (Figure 2. Because we assume that R/δ >> 1. p. Ya.19] . It means that σ r is of the order of pR. rather evident that there is a force acting on the surface of a ring joining the lid and the cylinder. as usual. The consideration of equilibrium across a radius gives the value of average stress σ ΘΘ (or simply σ Θ ): σ Θ (2Lδ ) = 2pRL or σΘ = pR δ [2.18] (since δ << R. The σ zz and all shear components are absent in the case of thinwalled items. We analyze the case when δ << R (the case named “thinwalled”).A. This force resists the action of internal pressure and it leads to the following equation for the stress component σ zz (or simply σ z ): pπR 2 = 2πRδσ z Then σz = pR 2δ [2.14). It is spherical lid of a vessel. we have a right not to distinguish outer and inner radii of the cylinder). it means that σ r is negligible in comparison with σ Θ .
The shape of a membrane in this case is defined as r = Rsinα Figure 2.(r / R) 2 ] 2 − 1 σ = ρgR (r / R) 2 1 [2.15 for a “unit” (or infinitesimal) square. Figure 2.16.5 HEMISPHERICAL MEMBRANE UNDER ITS OWN WEIGHT (FIGURE 2. Theory gives the following expression for the normal stress acting along the surface of the hemisphere: [1. σ. Hemispherical cup loaded by its own weight.15.16) We face this type of loading in many engineering constructions. Let the density of the membrane beρ. At the support ring (r = R) stresses must balance the total weight of the hemisphere and that is why σ = − gR is the maximal value of the principal stress. This problem (similar to that discussed above) relates to stress fields in shells or plates (membranes).20] where g is the gravitation constant. The third principal stress σ r << σ Θ and σ z and can be taken equal zero. . Both stresses σ Θ and σ z are principal as shear stresses are absent. especially when a spherical roof covers a large area of a stadium or a storehouse. Plane stress state in a wall of a cylinder.7. The thickness of a hemisphere is uniform and equal to δ (δ is taken as much smaller than R). 2. we come to the conclusion that there is a twodimensional (or plane) stress state in the wall of the cylinder as shown in Figure 2.28 Stresses Now.
This situation is interesting (and rather simple) because at very low values of the angle α the . Malkin 29 2. From the condition of static equilibrium.18) It is practical to analyze this situation because it applies to a socalled “coneandplate” viscometer.21 is applicable in this case if the condition δ << R is fulfilled.17) This is a model situation for many applications. torque. be much smaller than its radius. rotating or twisting of cylinders (inner or outer with no difference for the result). it is reasonable to assume that there is an average (constant) shear stress σ = σ Θz = σ zΘ over the wall section.A. Torsion (shear) of a long ple (iv)). The cylinder is loaded by the thinwall cylinder. As a result.7. as well as to scientific investigations. δ. In this case. used in the plastic and rubber industries. Let the wall of a cylinder. Ya.7 TORSION OF A CONE OVER A PLATE (FIGURE 2. the shear stress is given as: σ= 2M π(2R + δ ) 2 δ [2. R. one can derive: M = S(R + δ 2)σ where S ≈ 2π(R + δ 2)δ is the area of a ring (section of the cylinder). For example. Then this scheme reflects such a classical engineering situation as joining tubes with fitting.17. it is a scheme of a typical rotational viscometer widely used for measuring rheological properties of different substances. M. Eq 2.21] In the case under discussion.7. We analyze a case when the angle α between surfaces is small. a torque can be produced by relative turning.6 TORSION OF A THINWALLED CYLINDER (FIGURE 2. 2. (as in ExamFigure 2.
we come to the following relationship: σ(2πr)dz = πr 2dp or . loaded by pressure gradient.8 STRESSES IN A MEDIA MOVING ALONG A CYLINDER (FIGURE 2. This is the simplest and perhaps the most important hydrody n a m i c pa t t e rn h a v i n g general meaning for transportation of water. is practically constant throughout the volume of a material between the cone and the plate. Rotation of a cone over a plate.19. If to write the balance equation for the element of the length. between the cone and plate. oil products.30 Stresses shear stress. Integrating along the radius R gives the final relationship for torque and shear stress: [2. dp/dz. are very close to π/2.18. σ. Balance of forces gives the following expression for σ: σ=C sin 2θ [2. Movement of a medium along a cylinder. and in numerous other cases. dz.19) Figure 2. where C is a constant and the angle θ is taken from a vertical axis. then sin2θ ≈ 1 and σ = const. Values of θ throughout the gap.7.23] σ= 3M 2πR3 2.22] Figure 2. raw materials in the food and pharmaceutical industries.
24] where σ = σ zr = σ rz is the shear stress. this influence is associated with stress fields appearing in the neighborhood of a hole.19 says nothing about other components of the stress tensor. it is possible to find (we omit the details) that the distribution of stresses exists . though normal (diagonal) stresses definitely exist (at least pressure. and r is a current radius.A.25] and the stress distribution along the radius of the cylinder (or the tube or capillary) is linear: σ = σw r R [2. p. 2.20) Figure 2. Ya. p. Malkin 31 σ= r dp 2 dz [2.9 STRESSES AROUND A CIRCULAR HOLE IN A SHEET (FIGURE 2.20. A round (circular) hole is the simplest example of possible shapes of holes. Since practically all parts of engineering and everyday applications have holes of different sizes and shapes. In technical language.7. i. only pressure gradient (not pressure itself) influences the shear stresses. distance from the axis of the cylinder. σ w . stress is created around the hole. though holes can have different shapes.26] The diagram in Figure 2.e. If a sheet having a circular hole is stretched by a uniform load. The last equation shows that the shear stress at the wall. From the equation of equilibrium. creates alldirection compression). it is very important to know how these holes influence performance characteristics of a part. A circular hole weakening a flat sheet. (maximal shear stress) is calculated as σw = R dp 2 dz [2..
That is why stress is a physical object of tensor nature. of the hole are the most vulnerable (in respect of possible fracture) because the stress is three times higher than the average stress. It is always possible to calculate components of the stress tensor for any direction and to find principal directions and principal normal stresses. Calculations show that stresses decrease very rapidly away from the edge of the hole (in fact they are decreased as a function of (r0/r)2).8 CONCLUDING REMARKS Stress is the dynamic characteristic at a point and is defined as the relative force or the force related to the unit area.32 Stresses around the hole. 2. between the axis of the load action and an arbitrary direction. In the case shown in Figure 2. r>r0) and the angle. Stresses can be normal (perpendicular) and shear (tangential) to the surface where they act. X. The limiting values of σ Θ = σ ΘΘ are: σ = 3p at θ = π 2 and θ = 3π σ = − p at θ = and θ = π 2 [2. θ. If extension changes to compression (applied stress is equal to p).27] This phenomenon is called stress concentration (due to cracks) and larger stresses (in comparison with the average value) lead to weakening in bodies containing holes. the side points. where the stresses are maximal and equal to: σ ΘΘ = p(1 − cos θ ) (at r0/r = 1 other components of the stress tensor are absent). p. All components of the stress tensor depend on relative radius (r0/r) (r0 is the radius of the hole and r is a distance from the center of the hole. Most important is the situation at the hole boundary. Stress values depend on direction of the applied force and the orientation of a surface for which we wish to find forces acting at this surface inside a body. the latter .20. the maximal tension occurs at the points Y. and in this situation these points become the areas of likely failure.
Cauchy. Inst. Acad. Inst. Sur les équations differentielles d’équilibrium ou de mouvement pour le points matériels. Sci. But in many other cases. de Math. Mémoire sur les lois de l’équilibre et du mouvement des corps solides élastique. onedimensional. C. These combinations are called invariants. L. A. plane. 1827. Mémoire sur l’équilibre et le mouvement des corps élastiques. Cauchy. De la pression ou tension dans un corps solide. 4. They allowed us to find stress fields regardless of the particular properties of the material. Sci. 2. 3. Ex. Acad.A. L. 2. 1829.e. Mém. Navier.. Malkin 33 are extremal and shear stresses are absent at those directions. S. These equations represent the law of equilibrium (or balance) of all forces applied at a point.. Calculating stresses through a body is realized by solving differential equations with appropriate boundary conditions. Mém. France. 1829.. It leads to the necessity to take into account relationships between stresses and deformations.9 REFERENCES 1. A. 1827. it is necessary to analyze not only stress but deformation fields jointly. i. . The examples discussed above are typical due to simple (model) geometrical forms of bodies under analysis. Ya. rheological properties of matter. Concrete examples of calculations for some simple geometrical forms show that different situations are possible: uniform and distributed. Ex. one of which (sonamed spherical) is responsible for volume and the other (called deviator) for shape (or form) changes of a body (at a point). Poisson. de Math. France. or volume stress fields. The stress tensor can be divided into two parts. There are three special combinations of any arbitrary stress tensor which do not depend on choice of axes orientation in space. L.
we are interested in describing the changes occurring inside a body. The change of distances between points inside a body is transmitted to the neighborhood of a point which can be moni . The result of action of outer forces can be either movement of a body in space or change of its shape.A. and this phenomenon is called deformation. Here.1.1 DISPLACEMENTS AND DEFORMATIONS Figure 3. Malkin 35 3 DEFORMATION AND DEFORMATION RATE 3. change of shape can only occur if there are changes of distances between different sites inside a material. The change of a shape of a body is essentially the change of distances between different points on its surface. Ya. Thus. Displacement of two points in a body and appearance of deformation.
describe relative displacement. x2. x3). as could be expected for a tensor. The position of a site in a body is characterized by its radiusvector. and the distance between them now is ds′. As a result of some outer action. As a difference of two vectors. they both move and their new positions become A′ and B′.2] . because the initial length ds might be quite arbitrary. The values of all derivatives are dimensionless and they are expressed in absolute numbers or percents. deformation and relative displacement are tensors and components of these tensors can be calculated as derivatives du/dx. The absolute value of (ds’ − ds) is not important. Let the distance between two points A and B in a material be ds (Figure 3. the distance between points A’ and B’ is still infinitesimal. meaning that ε is a scalar. expressed as (dr1 . determined as ε= ds′ − ds ds [3.dr2) is a displacement. it is necessary to introduce two vectors: r1 for the point A and r2 for the point B. Relative displacement is characterized not only by its length but also by its orientation in space.1). because we have two sites. it is also a vector which can be expressed by its three projections: u(u1. The difference (dr1 .1] The definition 3. It is also pertinent that there are nine such values (three projections of vector u and three of vector x). u3). The quantitative determination of deformation can be accomplished by following the relative displacement of two vectors. It can be expressed through components of tensor of deformation (or strain). u. Since two vectors. If we assume that a body after deformation remains intact (between sites A and B). ε ij . the latter is of tensorial nature. only relative change of the distance between two sites. Accurate calculations of the components of the deformation tensor give the following expression: ε ij = 1 ∂u i ∂u j + 2 ∂x j ∂x i 1 ∂u1 ∂u1 ∂u 2 ∂u 2 ∂u3 ∂u3 + + + 2 ∂x ∂x ∂ x i ∂x j ∂x i ∂x j j i [3. and. r.dr2)/dr1. Indeed. u and x(x1. u2.1 is not tied to any coordinate system.36 Deformation and deformation rate tored by following the change of very small (infinitesimally small) distances between two points.
dij. are negligibly smaller than derivatives. In many cases. It is only true if deformations are small. Malkin 37 The complete expression for ε ij consists of linear (first parentheses) and quadratic (second parentheses) terms. In this Section we shall discuss only small deformations. and so on. and thus only the two first members (first parentheses) of the equation are essential. a gradient of u: g = grad u The result can be presented in the form of a matrix: . Ya. The large deformations (if the first derivatives in Eq 3. which enter into the second righthand member in Eq 3. This tensor. Relative displacement is definitely the cause of deformations inside a body.2 are not small) will be considered in a separate Section below. Are both displacement and deformation identical in this case? In order to answer this question. and that is why the tensor consisting only of first derivatives is called an infinitesimal deformation (or strain) tensor.A. derivatives in this formula are very small (<< 1) and their pair products.3] where the first line represents the projections of deformation along the x1axis.2. Hence they can be omitted. is as follows: ∂u1 ∂x1 ∂u 1 ∂u d ij = 2 + 1 ∂x 2 1 ∂x 2 1 ∂u3 ∂u1 + 2 ∂x1 ∂x3 1 ∂u1 ∂u 2 + 2 ∂x 2 ∂x1 ∂u 2 ∂x 2 1 ∂u3 ∂u1 + 2 ∂x1 ∂x3 1 ∂u1 ∂u3 + 2 ∂x3 ∂x1 1 ∂u 2 ∂u 3 + 2 ∂x 3 ∂x 2 ∂u3 ∂x 3 [3. by definition. let us calculate the relative displacement which is.
It is evident that the summation of du2/dx1 and du1/dx2 does not lead to deformation but to rotation of the body element.4] where the first line includes derivatives of the u1component of displacement along three coordinate axis. Figure 3. Two displacements. part of the tensor gij coincides with the deformation tensor dij. we need to understand the physical meaning of this difference or the meaning of the second.6] . as shown on the right diagram. It can be written in the following form: gij = dij + θij [3. Let us follow the deformation of a body element drawn as a rectangle. u2 and u1. socalled antisymmetrical.5] The first.but not deformation. but gij ≠ dij Then. and the third.2. It means that the second term in Eq 3. for the u3component of the vector u. The difference between them becomes clear if we decompose components of the tensor gij into two parts in the following manner: g ij = ∂u i 1 ∂ u i ∂ u j = + ∂x j 2 ∂ x j ∂ x i 1 ∂u i ∂u j + − 2 ∂x j ∂x i [3. It is quite evident that the tensors dij and gij are not equivalent. part of the displacement tensor. Now. socalled symmetrical.38 Deformation and deformation rate ∂u1 ∂x 1 ∂u g ij = 2 ∂x1 ∂u3 ∂x1 ∂u 1 ∂x 2 ∂u 2 ∂x 2 ∂u 3 ∂x 2 ∂u 1 ∂x 3 ∂u 2 ∂x 3 ∂u 3 ∂x 3 [3. having gradients du2 /dx1 and du1 /dx2. the second line is the same for the u2component. let us superimpose these two displacements.2 helps to explain the concept.5 represents rotation. may occur as shown in the central part of Figure 3.
which means that two neighboring sites (the distance between them being infinitesimally small) move with different velocities.2. at any point of a body. its gradient is calculated as . where θij consists of differences of the structure θ ij = 1 ∂u i ∂u j − 2 ∂x j ∂x i [3.A. 3. is the same. it means that a body moves as a whole and no deformation takes place. Superposition of two shear deformations leading to rotation. Ya. The deformation appears only as a consequence of velocity gradient at “a point”.2 DEFORMATION RATE If velocity (as a vector). If velocity is v (a vector value).7] and describes the rotations (turns) of infinitesimal volumes inside a body. Thus displacement at any point of a body is a sum of deformation and rotation. Malkin 39 Figure 3.
. and the gradient of velocity.9. The velocity is the rate of displacement. r. The relationship between gradient of velocity and gradient of displacement can be found from the equation: a ij = dv d du d 2 u d du dg ij = = = = dr dr dt drdt dt dr dt In the previous section. It means that in rotation of a solid body the gradient of velocity does exist but there is no deformation (because the body was assumed to be nondeformable).10] where Dij is the rate of deformation tensor. Differentiation in respect to scalar . The same is true for the deformation rate. Thus aij is a tensor determined by two vectors (v and r). The deformation is related to the first term in Eq 3. grad v = dv/dr. As in the previous case. Let us analyze the rotation of a solid (nondeformable) body around some axes. the rate of deformation tensor characterizes local changes of shape. The difference between tensors aij and Dij (similar to gij and dij) can be easily illustrated by a simple example. i. The velocity. only its symmetric part. from the axes is equal to ωr. d/dt.9] one obtains aij = Dij + wij [3. and wij is the socalled vorticity tensor. at a point located at the distance. Thus v = ωr.8] where space coordinates are described by radiusvector. v. while the vorticity tensor describes the rate of rotation of local elements of a body without their deformation. v = du/dt.e.40 Deformation and deformation rate aij = dv/dr [3. By decomposing tensor aij into symmetrical and antisymmetrical components. a ij = 1 ∂v i ∂v j + 2 ∂x j ∂x i 1 ∂v i ∂v j + − 2 ∂x j ∂x i [3. where ωis the constant angular velocity. .time. it was established that the whole gradient of displacement is not controlling deformation. . is evidently equal to ω.adds nothing new to the result. The reasoning is the same as above. r.
Two ways of realization large deformation of unispecimen length. Let a bar of the length lo be stretched by ∆l. The reasoning becomes much more complicated if ∆l is comparable with l. The socalled engineering measure of de fo rm a t i o n equals ε * = ∆l l = 0..1. i. Ya. But this approach to the definition of deformation contains an inherent contradiction.3 LARGE DEFORMATIONS The difference between small and large deformations depends on the value of derivatives in Eq 3.3. drawn in Figure 3. products of derivatives (in parentheses). it is always assumed that a reference state for deformation can be established. Certainly in this case we also can use an engineering measure of deformation as a characteristic of change of Figure 3. Malkin 41 3.A.3.1 (or 10%). If all derivatives are much smaller than 1. and it is axial extension. if ∆l = 1. Liquid does not have initial (or reference) state.e. and it is expressed as ε 11 = du1 dx 1 . using the model from Figure 3. Let us compare two situations. Then the deformation in the first step is ε 1 * = ∆l1 l o and ε 2 * = ∆l 2 l1 in the . In this sense. equal to 1 (or 100%). it is very easy to illustrate the essential difference between small and large deformations. for example. In the discussion of a concept of large deformations. the increase in the length occurs in two steps: initially by ∆l1 and then ∆l2. the quadratic terms can be neglected. That is why only materials having memory of their initial state are important here. Having such an approach.2. and the tensor dij is used instead of ε ij. flow of a liquid may not be considered as deformation because all states are equivalent.3: In the first case (case I). let lo = 1 and ∆l = 0. The simple question is: what is the deformation in this case? In the first case.
because if deformations are small. It is easy to note that in the example discussed above εH =εH I II i. some other values are used as a measure of deformations. because initial length of a sample in the second step is l1. In rheological literature.e. Then the complete deformation is the sum of both ε I *= ε1 *+ ε 2 *= 2 ∆l1 ∆l 2 l o ( ∆l1 + ∆l 2 ) + ∆l1 = + l o l1 l1 lo In the second case (case II). the quadratic terms in formulas for ε I * and ε II * are negligible in comparison to the linear terms. any function of deformation can be treated as a measure of deformation. the sample does not “know” which way it was brought to the final state. From the above. the increase of the length is achieved in one step. whereas calculations show a difference. as required.. Cij.42 Deformation and deformation rate second step. This appears only as a result of large deformations. it becomes apparent that there is a need to introduce such measure of deformation which does not depend on the order of operations. In fact. This increase is equal to (l1 + l2) and the deformation ε II* is calculated as ε II * = 2 ∆l1 + ∆l 2 l o ( ∆l1 + ∆l 2 ) + ∆l1 + ∆l1 ∆l 2 = l o l1 lo The ε I * ≠ ε II * contradicts the physical meaning of the experiment’s interpretation because the final result is not the same in both cases.11] Large deformations analyzed by this measure obey the law of additivity. One of the most widely used is the socalled Cauchy .Green tensor of deformation. the result does not depend on the history of deformation. and in this approximation (which is quite reasonable if ∆l1 and ∆l2 << lo) both measures of deformation become identical. Such measure is called a Hencky measure. defined by: ε H = ln( ∆l l) [3. It is directly related to the concept of large deformations ex .1 ε H .
as DY ∂Y = + Dt ∂t ∑ v k ∂Y ∂x k [3. as well. named the Finger tensor.12] where δ ij is the unit tensor (or Kronecker delta). It means that the behavior of a material in moving sites must be described because changes occur not at a point of a space but in a traveling element of a material which deforms along its re .2. Cij. and the CauchyGreen tensor is determined as: C ij = δ ij + 2ε ij [3.A. the problem is solved by using a socalled material or substantial derivative. D/Dt. the relationship between both is ij C ij C1 = δ ij ij Introducing different measures of deformations does not exclude the main question regarding the initial state . A similar situation has importance in classical hydrodynamics where transformation is followed (for example. For static states this problem can be solved by introducing the Hencky measure of deformations.Green tensor. The value of this question has been already demonstrated by the example of large deformations in uniaxial extensions. Another tensor of large deformations is frequently used. According to the definition. which can be written for any arbitrary variable. temperature effect or chemical reaction) in moving media. Malkin 43 pressed by Eq 3. not as a mathematical idea.point of reference of the deformed state. In such a case. The Cauchy . This is the tensor inverse (or reciprocal) to the Cauchy . C1 . but as a physical object which contains many “particles”. But the same problem appears and becomes more pertinent for a continuously moving medium where the position of deformed elements of a body is changing in time and we want to describe the process or the rate of deformation. Y.Green tensor characterizes change of the distance between two arbitrary “particles” in a “point”: here again we speak about a point.13] The main new approach which appears in the theory of large deformations concerns the importance of knowing the rate of deformation not only in a fixed coordinate system but in moving one. Ya.
one needs to use measures of large deformations and calculate their time derivatives. in some theoretical studies. The most popular are the Rivlin . the physical meaning of this operation requires us to calculate derivatives for a moving medium which follow time changes in a material point changing its initial position. Moreover. Bn(t). If deformation is large. An(t). In the case of the substantial time derivative. but on higher derivatives of deformation. tensors of the nth order. not on the rate of deformation only. Hence the general approach consists of formulating ideas concerning possible rheological behavior of a material for a moving (and deforming) element of a medium. certainly including laws of deformation. various special forms of time derivatives. As a result of large deformations. There are different mathematical ways to realize the idea of transformation of the rate of deformation tensor into a fixed coordinate system and. recalculating them into a fixed coordinate system. Similar to our discussion of large uniaxial extension. and then comparing the results with an experiment.Eriksen. This concept is called the principle of material objectivity and it states that all physical phenomena. They are used if it is assumed that rheological behavior of a material depends. and White Metzner.2 They are determined as . there is a necessity to introduce kinematic tensors of a higher order hich are determined as time derivatives of the CauchyGreen or Finger ten sors.13. material elements can travel far away from their initial position. An observer who measures properties of a material is always positioned in fixed (unmovable) coordinate system. In Chapter 7. This is completely true for the rate of deformation. devoted to properties of viscoelastic materials. generalized by Eq 3. This problem in the theory of large deformations is solved by introducing time derivatives of a different type. D/Dt. must not depend on a coordinate system used for their mathematical formulation. as well. it is also important here that the choice of different reference states must not lead to an ambiguous estimation of deformation. and that is why it is important to apply proper rules of transition from the reference state. their behavior is modeled by equations containing a sum of nth order time derivatives of deformation (socalled rheological equations of a differential type). depending on the choice.44 Deformation and deformation rate placement.
d2. respectively. A*C*. And the sphere itself has transformed into an ellipsoid with semiaxes of lengths (1 + d1)dr. the directions of the radii AB.10 and for liquids. and (1 + d3)dr. respectively.4) with a center positioned at a point A and radius of the sphere dr (infinitesimal small length). the following changes have taken place in a body: the point A has moved to a new position A*.8 More recently. It can be illustrated by a very spectacular picture of deformations in the vicinity of some point. and d3.4 PRINCIPAL VALUES AND INVARIANTS OF THE DEFORMATION TENSORS The principal deformations (strains) are calculated in the same way as principal stress. are extensions along three orthogonal directions.11 The use of various measures of large deformations and different types of their time derivatives allows one to arrive at qualitative predictions concerning possible effects in rheological behavior of a material. but it is the task of an experiment to find a model which can adequately describe physical phenomena observed for different real materials. A complete treatise on modern theories of large deformations of solids is included in book by Green and Adkins. and x3. For this aim. 6 and Jaumann. and AD have changed to the directions A*B*. Rivlin9 discussed studies on large deformations in numerous publications. x2. As a result of movements and displacements. Ya. let us represent an infinitely small volume in a body as a sphere (Figure 3. Later ideas of the theory of large deformations were discussed and developed by Finger. (1 + d2)dr. by Lodge. d1. and A*D*. respectively.7 Fundamental works were also contributed by Biot. The coordinates of the central point A are x1.A. Malkin 45 A n (t) = and D n C ij (t) Dt n Bn (t) = − D n C1 (t) ij Dt n where Cij and C1 are the CauchyGreen and Finger tensors.5 Cosserat. the principal deformations. ij SaintVenant3 was the first who realized the necessity to consider the concept of large (finite) deformations.4 Zaremba. 3. For the infinitesimal deformation tensor. AC. .
1 [3. If deformations are small and it is possible to neglect quadratic terms in comparison with linear terms. The deformations characterize the change of the shape of a volume element of a body — transition from a sphere to an ellipsoid.e. Transformation of a sphere into an ellipsoid as a consequence of three principal deformations along their axes.16] i.4. and the invariants do not depend on the coordinate axes. Besides they determine the relative change of the volume.15 gives a particularly evident result: ε v = d1 + d2 + d3 [3. which can be written as follows: εv = V ell − Vsph Vsph [3. . ε v . the Eq 3..46 Deformation and deformation rate Figure 3. volumetric changes are equal to the first (linear) invariant of the tensor of infinitesimal deformations and that is the physical meaning of the latter.14] Simple calculation shows that ε v = (1 + d1)(1 + d2)(1 + d3) .15] It is very easy to show that ε v is expressed through invariants of the deformation tensor because change of volume must not be associated with the choice of the coordinate system.
Let the length of its edges be a. oriented along the principal axes. Then the extension ratios are: λ1 = a * a. λ 3 = c * c and the volume change is calculated as ∆V + V a * b * c * = = λ 1λ 2λ 3 V abc The last formula allows one to state a very simple rule of constancy of volume in deformations of any type: λ 1λ 2λ 3 = 1 [3. λ 2 = b * b. one can write du 1 du ε 11 = 1 + 1 dx1 2 dx1 1 1 = (λ − 1) + (λ − 1) 2 = (λ2 − 1) 2 2 2 [3. Ya. at a some site in a body. we can write: d ij = εv δ ij + d (dev) ij 3 where the second member in the righthand part of the equation is a deviatoric part. λ.18] . be (∆l + l0) /l0. b and c before deformation. can be decomposed into spherical and deviatoric parts. and become a*.A. For this purpose. and c* as a result of deformation. b*. d (dev) . Malkin 47 The volumetric changes in deformation can also be represented through extension ratios. 3. the deformation tensor. POISSON RATIO Let a bar of sufficient length to be stretched and increase its length by ∆l/l0 or the extension ratio. let us (conditionally) cut out a small rectangular parallel pipe.1. Considering that the first invariant is the volume change.17] Like any other tensor. dij.5 UNIAXIAL ELONGATION. of the dijtensor which describes shape transformation occurring ij without changes in volume. If (du1/dx1) = λ .
5. let the bar have a round crosssection with the radius. and. For simplicity. If its elongation is ∆l. For real solid materials. independent property of a material.5. The relative change of volume ∆V/V is ∆V V= (ro + ∆r) 2 (l o + ∆l) − ro2l o ro2l o [3. µ. is: µ= ∆r ∆l ro lo [3.21. µ < 0. then.48 Deformation and deformation rate Additional to being stretched in the axial direction. radius is decreased by ∆r. into spherical and deviatoric terms for uniaxial extension. the last formula gives ∆V V = (1 − 2µ ) [3.5. by definition. and the length. From Eq 3. It is interesting to use the general method of decomposing the deformation tensor. If λ << 1. lo. and deformation is equal toε. Only for some rubbers µ = 0. the deformation tensor for such case can be written as: . resulting from uniaxial stretching. one can see that deformations occur without volume changes when and if µ = 0.20] If ∆l << lo and consequently ∆r << ro (small deformations). meaning that their elongation is accompanied by increase in volume. ro. The relation between relative changes of dimensions in the lateral and axial directions cannot be established on the basis of a purely geometrical picture of deformations because this relation is an inherent.19] It is now easy to calculate the volume change.21] Poisson ratio is a measure of volume changes during small deformations. as a result of stretching. the Poisson ratio. The quantitative characteristics of this property is the ratio of relative lateral contraction to the relative longitudinal extension and this special property of a material is called the Poisson ratio. dij. the bar undergoes changes in the lateral direction.
however. takes place. Malkin 49 ε 0 0 2 0 0 µε 0 = 1 − 2µ εδ + 1+ µ ε 1 0 d ij = 0 0 ij 3 3 0 0 µε 0 0 1 The structure of this sum is very similar to the structure of the stress tensor decomposition into two parts (compare with the analogous procedure in Chapter 2).6 SIMPLE SHEAR AND PURE SHEAR Simple shear is a very important type of deformation because movement of all fluids and liquidlike materials is based on the principle of sliding of neighboring layers relative to each other. For example.22 is converted to an ordinary condition such that µ = 0. let the bar be stretched by 9 times (it is quite possible for rubber ribbons or melted fibers).2 is not valid. Ya. and formal definition 3.A. but in the more general case it is not true. A similar approach will also be taken in the next Chapter for the discussion of elasticity theory.5 as a necessary condition for constant volume at extension) to the range of large deformations must not be done in a straightforward manner. according to Eq 3. respectively.20 shows.20. Eq 3. is determined by the slope which will be denoted as γ: .19 for the Poisson ratio. Indeed. It means that ∆l lo = 8 and the volume can remain unchanged if the final radius becomes equal to 1/3 of its initial value. u1. preserving the formal definition 3.22. This example shows that adaptation of infinitesimal deformation mechanics (µ = 0. are shown in Figure 3. a displacement. More precise analysis of Eq 3. Then ∆r / ro = 2 3.5. du1 dx2. Its gradient. and in the general case of arbitrary deformation. that for large deformations Eq 3. µ = 1 12. we have for ∆V/V=0: 1 − 2µ(1+ ε ) + µ 2ε (1+ ε ) = 0 [3. 3.5 a and b. In this case according to Eq 3.5 as the condition for maintaining the constant volume at stretching has no general meaning. Along the direction of shear marked by an arrow.22] If ε << 1. The schemes of simple shear for an element of a body in the case of small deformations. and the rule of µ = 0.19.
5 b in which the components of the tensor. It is related to the change in the length of the segment OA. appears. The appearance of a diagonal component in the deformation tensor in a simple shear is a direct consequence of large deformations because ε 22 is proportional to γ 2 and its value becomes negligible if γ << 1. which were oriented before deformation in the x2direction. Small (a) and large (b) deformations in simple shear. observed in twisting of wires: their length slightly changes in this case. u2 . which after displacement now becomes OA*: OA * − OA = 1+ γ 2 OA ( ) 1 2 −1 [3.50 Deformation and deformation rate γ = tanα = du1 dx2 Since the length of linear elements.23] The value of γ = du1/dx2 for simple shear determines all components of the tensor at large deformations. and the observed change of the length in the axis direction is . This tensor is graphically illustrated in Figure 3. are marked by arrows (factor 1/2 is omitted in drawing this Figure). Twisting is an example of shear deformation. According to the deformation of the ε ij tensor.5. one more displacement component. ε ij . This phenomenon is known as the Poynting effect. its components are: 1 ε 12 = ε 21 = γ 2 ε 22 = 1 2 γ 2 Figure 3. is changed in shear.
Components of the Cauchy . along the principal directions). λ 2 .A. and the orientation of the principal axis is calculated as 1 β = atan( γ 2 2) [3. not only the lengths of linear elements change (e. of the diagonal from OC to OC* position.Green tensor in shear are important for theoretical discussion concerning rheological models of elastic liquids. Calculations give the following expression for Cij: 1 γ γ 1+ γ 2 C ij = 0 0 0 0 1 In a simple shear. x1. between the direction of shear. they are as follows: γ 1 = cotβ. γ 2 = (λ22 − 1).g. The angle. θ.25] where λ 1 .5.and λ 3 are principal elongations (or extension ratios in the directions of principal axes). where the angle of turn (rotation). β.17. but rotation of the elements of a body also takes place. γ 3 = (λ2 − 1) 3 2 2 2 [3. These values are related to the angle β in Eq 3.24. and γ 3 = 1 A result obtained from the last set of formulas for λ i indicates that in simple shear no volume change occurs because γ 1 γ 2 γ 3 = 1 in accordance with Eq 3.24] The main components of the deformation tensor may be written as follows: 1 1 1 γ 1 = (λ11 − 1). .. Ya. Let us now discuss some models of simple shear which are often used in rheological literature and are illustrative for the tensorial nature of the deformation tensor.5). This effect is illustrated in Figure 3. Malkin 51 restricted to ε 22 component of the deformation tensor. γ 2 = tanβ. and to the plane deformation state (as in Figure 3. is shown.
and α is its gradient. is based on definition of the ωij from Eq 3. into new position A*B*.5 is applicable. because an act of deformation involves certain volumes which may include a large number of molecules or their constituent parts. Geometrical image of a pure shear is drawn in Figure 3. parallel to its initial position. Scheme of pure shear.7. AA*. no element of the body undergoes rotation. is due to displacement. and the diagonal OM does not change its position at all. It means that pure shear can be considered (and can be realized) through the superposition of two uniaxial extension deformations (with different signs). That is why rotation in simple .5. which in general form is expressed by Eq 3.6.6. It is seen that ωij = 0 if all differences of the displacement gradient equal zero. This case. For small displacement. For the simple shear. unlike for large deformations. due to deformation. being only extended to OM*. But in real materials this difference can appear to be essential. called pure shear.θ = α 2. where the general Eq 3. must be used. Figure 3. since deformations occur in the Figure 3. in this Figure. From the point of view of continuum mechanics. It is quite evident that the transition from the square OAMB to the rhomb OA*M*B* can be achieved by pressing the square along the direction AB. Any gradient of displacement consists of deformation and rotation.6 can be obtained in a different way.52 Deformation and deformation rate Shear deformation. therefore. infinitely small volumes “at a point” and the rotation of infinitesimal elements of a body as a whole has no effect on its deformation. the difference between simple and pure shear is not significant. In pure shear the diagonal AB of the small square (at some point) moves. the angle of rotation. with simultaneous stretching along the direction OM. this condition has following form: du1/dx2 = du2/dx1. It is possible to find such shear conditions where no rotation occurs.
3. Ya. the length after deformation l. it is especially important to know the components of complete deformation. orientational extension of fibers) and everyday life. lateral contraction takes place. Now.A. only for homogeneous deformation fields. we shall summarize the main relationships describing deformation. as mentioned above. Let the extension ratio of a uniform bar loaded along its axis be equal to λ (initial length lo.1).1 UNIAXIAL EXTENSION OF A BAR (BEAM. The deformation can be found. the calculation of deformation fields cannot be carried out for an arbitrary scheme of loading because reaction of a material to an external force depends on inherent properties of a medium and its geometrical size and shape. ε *. and its value is determined by the Poisson ratio ε 22 = ε 33 = − µε 11 = − µε * In some cases. is (λ . regardless of rheological properties of a material.. and here we shall summarize the main results. Some principle examples have been already discussed in the preceding Sections of this Chapter.7. The engineering measure of deformation. the extension ratio λ = l/lo). for example. The same force creates unlimited deformation in a liquid and only small deformation in a steel object. If ε * << 1 then ε 11 = ε * In uniaxial extension. Malkin 53 shear does influence the rheological behavior of deformable (in particular flowing) materials and is taken into consideration in formulating laws of deformations in the form of time derivatives used to calculate the rate of deformation. That is why calculation of deformation is possible only for materials having established properties.g. FIBER) It is one of the most frequently met cases in technology (e. if we wish to divide the full deformation into plastic and elastic parts (such problem is pertinent to fiber spinning technology where . 3.7 EXAMPLES Unlike stress analysis. Stress analysis of uniaxial extension was discussed in Chapter 2.
such as paints. Besides.7. colloids. depending on the Poisson ratio. clay. .Green and Finger methods of large deformation calculations are widely used.54 Deformation and deformation rate the main goal is to produce highly oriented fibers). liquidlike and plastic materials. cutting and threading are operations in which shear plays a dominant role. Shear rate. Such flow occurs in a very thin gap between two parallel surfaces. polymer solutions and melts. ε 11 component of the deformation tensor has the following structure: ε 11 = ε * + 1 2 1 1 ε * = (λ − 1) + (λ − 1) 2 = (λ2 − 1) 2 2 2 In applications of the theory of large deformations to rubbers and rubbery polymeric solutions. It is necessary to use the measure of deformation which is additive to the prehistory of loading and the Hencky measure of deformations. C1 = λ2 11 Other components of Cij and C1 tensors are expressed through deformations. the Cauchy . to satisfy the requirement. v. ε H . as already discussed. 3.2 SHEAR Shear deformations are very typical for all hydrodynamic problems. including the flow of low viscosity liquids (water. Main theoretical results concerning large deformations in shear were discussed in detail in the last section of this Chapter and need not be repeated. and many others. gasoline). may have variable impact even under the same geometrical conditions and stress. depending on rheological properties of a medium. many engineering applications rely on shear: twisting of bars and tubes. Hence. determining peculiarities of flow. For uniaxial extension ε H = ln(1+ ε *) = lnλ In the case of large deformations. sealants. Their values in our case are as follows: C11 = λ2 . oil. with one of them fixed and the other moving with constant velocity. ij ε 22 and ε 33 . only for homogeneous flow can the shear rate be estimated beforehand.
A. Ya. Malkin
55
This condition is typical for flow in narrow gaps of bearings, and more important, it is widely used for measurement of rheological properties of various liquids in socalled rotational viscometers. If the width of a gap, h, between surfaces moving in parallel to each other is & small, the shear rate, γ, in a flowing liquid is calculated as & γ = v/h This formula also applies when both surfaces are curved but the size of the gap is much smaller than the radius of curvature; for example, if flow occurs in a very narrow gap between two coaxial cylinders, one of which is rotating with constant velocity.
3.7.3 PLANE DEFORMATION (STRAIN) STATE
Plane (twodimensional) stress and deformation (strain) state appears in thin items, stretching films, membranes, shells, and so on. The stress fields for some typical situations have been analyzed in Chapter 2. The calculation of the deformation field, regardless of rheological properties of matter, can be performed for homogeneous static (equilibrium) state (e.g., a sphere (balloon) filled with gas, having known pressure, up to the certain size). Let the initial radius of a balloon be Ro, and after increase of inner pressure the radius becomes R. The initial width of a cover is δ o and δ o << Ro. The extension ratio equals λ = R/Ro. The directions along the radius of a sphere and tangential to its surface are principal directions because shear stresses and deformations are absent in thin shells, as discussed in Chapter 2. The surface of the cover increases as a result of deformations, and for (R − Ro)/Ro<<1 we have: ε 2 = ε3 = r − Ro = λ −1 Ro
where the directions 2 and 3 are tangential to the surface of the cover. The third principal deformation, ε 1 , (the direction 1 is along the radius) can be calculated using Eq 3.21, considering volumes of a material before and after deformation. It is easily seen that in the case under discussion
56
Deformation and deformation rate
∆V/V = 1  (R2δ/R 2δo) o It means that R 2δ and δ δ o = 2µ(R o R) 2 = 2µ λ2 R 2δ o = 2µ o
Then ε 1 = (δ − δ o ) δo = 2µ −1 λ2
If volume of a material under deformations is constant (for example, if the cover is made out of rubber), µ = 0.5 and we have ε1 = 1 −1 λ2
3.7.4 THREEDIMENSIONAL DEFORMED STATE
Many engineering applications can benefit from analysis of these relationships. Important to note is that consideration must be given to the real rheological properties of the material in question. Some general principles are worth citing because they apply to analysis of large deformations of rubbers. If the values of principal extension ratios are λ 1 , λ 2 ,and λ 3 , or the engineering deformations along principal axes are ε i *= λi −1 then the values of the CauchyGreen and Finger tensors are:
A. Ya. Malkin
57
C1 = λ2 ; C 2 = λ22 ; C3 = λ2 1 3 C1 = λ2 ; C1 = λ2 ; C1 = λ2 1 1 2 2 3 3 The first invariants of C and C1 tensors are C I = (λ 1λ 2λ 3 ) 2 and C1 = (λ 1λ 2λ 3 )2 II As discussed above (see Eq 3.17), the equality λ 1λ 2λ 3 = 1 means that deformation proceeds without changes of volume. Hence the condition of constant volume in threedimensional deformations of arbitrary type is: CI = C1 = 1. II
3.8 CONCLUDING REMARKS
Action of outer forces results in displacement of the points of continuum. If displacements are inhomogeneous throughout a body, and relative displacements appear, they lead to deformations, which are the consequence of changes of infinitesimal distances between different points inside a body. Displacement is a vector, but relative displacement and deformation are objects of tensorial nature, because to describe them both it is necessary to operate with two vectors. The relative displacement is described by a radiusvector of two points for which displacement is considered, and the deformation by a vector of displacement and a radiusvector of a point, where the displacement occurs. Deformation is only a part of relative displacement, which also includes rotation of elements of a body as a whole. Deformations can be small (or infinitesimally small) or large. The boundary is determined by the value of relative displacement (or gradient of displacement), which is a dimensionless value. If this value is small (<< 1), it is reasonable to neglect the square of this value in comparison with the value itself. One can thus neglect all quadratic terms included in the relationship. In this case, deformations can be treated as infinitesimally small. If large deformations are considered, some new effects appear. First of all, physical phenomena occur at a site which moves and during deformation vacates its initial position. Description of all occurrences (including deformation itself) must be done in relation to a moving point. An observer, carrying out experiments with a material, follows its behavior and treats the results of measurements in a fixed coordinate system. Hence it is necessary to know the rules
58
Deformation and deformation rate
of transformations and the tensor values used for projecting deformations from a moving to a fixed coordinate system. Large deformations are characterized by special measures of deformation, such as the Hencky measure (a logarithmic measure subjective to additivity rule), Cauchy  Green, and Finger tensors of large deformations. Time derivative of displacement of a point is its velocity, time derivative of relative displacement is a gradient of velocity, and time derivative of deformation is rate of deformation. Time derivatives of tensors are also tensors, and for calculation of the rate of deformation, special rules exist which take into consideration large deformations and movement of a deforming site in space. Gradient of velocity is a sum of rate of deformation and vorticity tensor as elements of a body which can not only deform but simultaneously rotate it. In the process of uniaxial longitudinal extension, a body undergoes lateral compression. The ratio of relative changes of lateral and longitudinal sizes is called the Poisson ratio, which is an inherent property of a material. For the range of small deformations the volume of a body remains unchanged if the Poisson ratio equals 0.5, but in large deformations this simple rule is not obeyed. There is a special interesting case of deformation when volume changes are not taking place, which is a simple shear. At large shear deformations, diagonal components of the deformation tensor appear, and they lead to some effects of a second order, such as elongation of long items at their twisting (Poynting effect). Simple shear is accompanied by rotation of elementary volumes in space. It may reflect behavior of a material. In order to exclude rotation, it is necessary to apply pure shear in which rotation does not exist. This type of deformation is equivalent to a twodimensional situation of superposition of extension and compression in mutually perpendicular directions.
3.9 REFERENCES
1. 2. 3. 4. 5. 6. H. Z. Hencky, Angew. Math. Mech., 5, 144 (1925). Concept introduced by G. Kirchhoff, Acad. Wiss. Wien Sitzungsberichte, (IIa), 103 (1894). J. L. White and A. B. Metzner, J. Appl. Polym. Sci., 7, 1867 (1963); J. L. White, J. Appl. Polym. Sci., 8, 2339 (1964); Rubber Chem. Techn., 42, 257 (1969). A. J. B. de St. Venant, Mémoire sur équilibre des corps solides, dous les limits de leur élasticité, et sur les conditions de lèur resistance quond es désplacements êpouvés par leurs points ne sont par trés petit, C. R. Acad. Sci., Paris, 24, 1847. J. Finger, Acad. Wiss. Wien Sitzungsberichte, (IIa), 103 (1884). S. Zaremba, Bull. Int. Acad. Sci., Cracovie, 594, 614 (1903). F. Cosserat, Thèorie des corps deformable, Paris, 1909.
A. Ya. Malkin 7. 8.
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G. Jaumann, Acad. Wiss. Wien Sitzungsberichte, 120, 385 (1911). M. Biot, Theory of elasticity with large displacements and rotations, Proc. 5th Int. Congr. Appl. Mech., 1939. 9. R. S. Rivlin, Phyl. Trans. Roy. Soc. Lnd., Ser. A, 240, 459, 491, 509 (1948); 241, 379 (1949); 242, 173 (1950); 243, 251 (1951); Proc. Roy. Soc., A195, 463 (1949). 10. A. E. Green and J. E. Adkins, Large Elastic Deformations, Oxford University Press, London, 1960. 11. A. S. Lodge, Elastic Liquids, Academic Press, London, 1964.
A. Ya. Malkin
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4
RHEOLOGICAL EQUATIONS OF STATE
4.1 MAIN RHEOLOGICAL EFFECTS
The concept of rheological equation of state (or constitutive equation) occupies the central position in modern rheology. It is a relationship between stresses acting at a point and deformations occurring as a result of their action. Such a relationship determines all mechanical phenomena which can be expected in the observation of mechanical behavior of a material. Rheological equations of state serve the purpose of understanding and describing qualitatively and (the most desirable) quantitatively various “anomalous” effects observed in real life for real materials. Some macroforms of these effects were mentioned in Chapter 1 and they are now described in rheological language in terms of stresses, deformations, and rates of deformation. The number of various rheological “anomalies” is large; any kind of deformation of material which does not obey the simplest, classical rheological equations (Newton and Hooke Laws) inevitably leads to different, new qualitative, or at least quantitative, phenomena which are not described by the concept of a Newtonian fluid and a Hookean solid body. Each of these phenomena can be considered as a “rheological effect”. However, there are several fundamental experiments which definitely indicate that material is either “classic” or “rheological”. These experimental observations are discussed below.
it is important to know how apparent viscosity changes when shear rates (and stresses) are changing in a very wide range. γ. & & and then carry out measurements at different values of σ or γ.1. Sometimes. and such effect is frequently called shear thinning.62 Rheological equations of state 4. and it is called apparent (or nonNewtonian) viscosity. & & η − σ .1. In order to make this dependence more visual. The & graph constructed in logγ . is used.1. Liquids having con& stant viscosity for any γ are called Newtonian liquids and their viscosity is called & Newtonian viscosity. the ratio σ γ is not constant. η(γ ) .1 NONNEWTONIAN VISCOSITY & If we define viscosity.1 as a ratio of shear stress. It can be displayed in any of three coordinate systems. by Eq 1. but viscosity can also increase with shear rate increasing (the socalled shearthickening).a. as shown in Figure 4. This is the most typical case. The apparent viscosity decreases in this example. η. . and shear rate. η − γ .c. In many applications.logσ coordinates is also called a flow curve. & therefore measurement points fulfill the condition of constancy of the σ γ ratio. Different images of a flow curve: dependencies η(σ ) . & & Figure 4. σ. Dependence of the apparent viscosity on shear stress or shear rate is called flow curve. η.or σ − γ .b and σ (γ ) . the ratio σ γ should be constant because viscosity is a property of liquid. viscosity decreases or increases (for the same material) in a different range of shear rate. The flow curve of any Newtonian liquid is a straight line inclined by 45o to both axis. In many real cases. logarithmic scales are frequently used. even though the same symbol.
though it appears in different forms: as a gradual decrease of apparent viscosity in Figures 4. Some authors continue & to call the ratio σ γ a structure viscosity (struktur Viskosität 1 ). NonNewtonian behavior of a liquid was.3. Upper line . Concentration of the polymer in weight percentage as labeled.2.flow curve of a pure solvent.3 for polymeric systems and in Figure 4. Flow curves of polybutadiene solutions in methyl naphthalene. Ya. All other curves are drawn for solutions. In all cases shown in these Figures.2 and 4. even though the origin of this effect is not necessary related to the rupture of a “structure” of a flowing liquid. .flow curve of a pure polymer. and was explained by the changes of a structure of colloid as a result of deformation. for the first time. T = 25oC. Some typical examples of nonNewtonian behavior are given in Figures 4. observed by Ostwald1 for colloid dispersions.4 for a bentonite solution.A. Malkin 63 Figure 4. Lower curve . the effect of nonNewtonian flow is very pronounced.4.2 and 4. and as a sudden jump from very high to very low viscosity in Figure 4.
Experiments conducted for a typical polydisperse polymer. which are important to consider in interpretation of the physical meaning of nonNewtonian behavior and in quantitative description of a flow curve. Melt index of a sample was 2 g/10 min. The value of apparent viscosity at & these high shear rates and stresses (formally at σ → 0 and γ → 0) can be called upper. At low shear & rates (formally at σ → 0 and γ → 0).2 are typical of polymer solutions. . limiting. In rather dilute solutions. One of the main problems in description of flow curves is the existence of limit& & ing values of apparent viscosity at σ → 0 or γ → 0.typical of nonNewtonian behavior. T = 150oC. flow curves display three regions. The solvent used behaves like a Newtonian liquid (flow curve is a straight line inclined by 45o to both axes). Finally. or minimum Newtonian viscosity. Flow curve of a polyethylene melt. Newtonian behavior is observed (straight line inclined by 45o to both axes). and apparent viscosity corresponding to this region of a flow curve is called zeroshear or initial or maximum Newtonian viscosity.64 Rheological equations of state Figure 4. the upper part of a flow curve again has Newtonian behavior. Flow curves in Figure 4. Then the decrease of apparent viscosity (declining from the straight line) is observed .3. and at σ → ∞ and γ → ∞.
There is no doubt that the initial Newtonian viscosity region exists for all.. After L.95 mPas) and at σ → ∞ (η= 9.3 MPas) are shown. A. 184 . Ya. Rehbinder. The general reason for this is a loss of flow stability at high shear rates (a very close analogy of this behavior is a wellknown transition from laminar to turbulent flow for regular liquids).A. This behavior is particularly strong for a pure polymer. solutions. A. but undoubtedly these experimental observations demonstrate peculiar rheological properties of these media. Further increase of polymer concentration leads to increasingly more noticeable deviation from Newtonian behavior.195 (1955). A continuous and gradual decrease of apparent viscosity occurs in a . and N. is apparent. Highly concentrated solutions (30% and higher) have a broader range of nonNewtonian behavior. Malkin 65 & Figure 4. including very concentrated. Also. It may be argued whether this region of the graph corresponds to real flow with rapid decrease of apparent viscosity or it reflects other. Kolloid Zh.logσ and η − σ coordinates). at low shear rates. the upper Newtonian region of flow curves cannot be reached (or maybe does not exist) for concentrated solutions. special type of behavior of a material. SerbSerbina. Limiting values of apparent viscosity at shear stresses σ → 0 (η = 0. N. though in all cases the Newtonian viscosity. 17 (3). Another example of rheological properties is represented in Figure 4.4. followed by the flow curve which becomes close to a vertical line.3 for polymer melt. P. NonNewtonian viscous behavior of 10% suspension of natural bentonite (in logγ . Abduraghimova.
viscosity drops by 8 decimal orders of magnitude. The flow curve in Figure 4. it is very difficult to find a proper assignment for experimentally observed viscosity versus shear stress dependence of real materials rapidly changing their structure under deformation. Figure 4. The initial Newtonian region in the flow curve appears in this Figure only as a hint. In many cases. the following equations are frequently applied: Cross equation:2 Carreau equation:3 Yasuda et al. are called viscoplastics. For the flow curves with distinctly expressed range of initial Newtonian viscosity.4 can be treated as a flow curve of a nonNewtonian liquid with rapid viscosity decrease or as a dependence of apparent viscosity on shear stress. by several decimal orders of magnitude. it may even be suspected that this branch does exist. characteristic for viscoplastic bodies. at sufficiently high shear stresses to cause flow. or in a narrow range of shear stresses. in other regions. The magnitude of ηo exceeds the apparent viscosity.95 MPa⋅s to 9.1] [4. Both definitions are reasonable. The materials having sharp transition from solidlike to liquidlike behavior. ηo . and only the part of the flow curve at σ > σ y as the flow curve. can also be found here as a limit of η at σ → 0.4 represents a flow curve with a very sharp drop of viscosity at some value of shear stress. equation:4 η= ηo & 1+λγm ηo η= & [1+ (λγ ) 2 ]p ηo η= & [1+ (λγ ) a ](n1)/ a [4. from 0.3 mPa⋅s. The transition through σ y might be considered as a transition from solidlike to liquidlike behavior. That is why it is reasonable to treat the behavior of a material at σ << σ y as solidlike (even though the material is a liquid and flows even though its viscosity is very high). and the transition stress is called yield stress (or yield point). In fact.3] . The whole decrease of apparent viscosity exceeds 1000 times in comparison with the initial value. σ y . both on theoretical and empirical levels. Many attempts were made to describe flow curves of various materials by analytical functions of different type.66 Rheological equations of state very wide range of shear rates. The initial Newtonian viscosity.2] [4.
and the minimal value of apparent viscosity at γ → ∞ is frequently observed. only a part of deformation is related to the flow.1 and 4. rate of irreversible deformation. not as a rate of full deformation.2. At sufficiently high values of shear rate. depending on shear rate. in comparison with ηo . in transient flow. In many cases. The flow curve measurements have various applications. γ must be treated.4. It is interesting to & emphasize two main peculiarities of these equations: all have a limit at γ → 0 equal to ηo . the rate of this deformation must be taken into account in calculating viscosity. Two of them are of primary value. They differ in a number of parameters: two in Eqs 4. It means that it was assumed that there is a great decrease in apparent viscosity. i. they transit to the socalled power law (Ostwald . nothing is changing in this case. relatively dilute polymer solutions) when the total decrease in apparent vis& cosity is not large. and three in Eqs 4. In some cases it is important to consider viscosity in transient regimes of shear deforma& tions. All the equations are similar in their structure. it is important to note that the definition of viscosity applies to steady flow (no timerelated changes). at very high shear rates. If the deformation is reversible (elastic).in . it has nothing in common with viscous flow and definition of viscosity.. when shear rate increases.3 and 4.de Waele equation). it is always necessary to know viscous properties of a real material to solve any hydrodynamic problem related to flow of the material . Discussing the problem of apparent viscosity. Thus. flow instabilities of a different kind appear. First.6 which can be written as & σ = Kγ n [4. so that the limiting value of & apparent viscosity at γ → ∞ is negligibly small. Malkin 67 Vinogradov . & All equations show that. Ya. η is apparent viscosity.Malkin equation:5 η= ηo & & 1+ Aγ + Bγ 2α α [4. There are situations (for example.4] In all equations. In other cases.5] where K and n are empirical parameters.e. the possibility to reach the limiting viscosity is restricted because. at γ → ∞. all other symbols are empirical or semiempirical constants. apparent viscosity diminishes to zero. ηo is zeroshear viscosity. For pure viscous liquids. but only as a rate of flow.A.
to design processing equipment and predict conditions of its use in practice (e.5. and paints. Second. calculation of rate of flow and pressure drop). and it decreases in a very narrow range of shear stress near σ y .4).1. the flow curve reflects chemical content and/or physical structure of a material.. Figure 4. is characterized by a rapid change of viscosity at σ → σ y (Figure 4. It predicts the decrease of apparent viscosity in the flow range: .68 Rheological equations of state particular. this pat& viscoplastic medium in γ − σ (a) and η − σ (b) coorditern of behavior is very close to nates. sealants . For some materials. and η p and K are empirical constants.2 PLASTIC BEHAVIOR Viscoplasticity can be formally treated as a viscous flow: viscosity is infinite at σ < σ y .6. rubber compounds.8] where σ y is the yield stress.7] [4. For other materials . The yield stress. Plastic material cannot be deformed at σ < σ y . and it flows at σ > σ y . such as many pa st e s. and as such it can be used as a method of analysis of material quality.5). 4. polymer melts containing solid filler.g. Formal description of viscoplastic behavior is based on a model of abrupt jump of viscosity at σ y and existence of yield stress. g re a se s.for example. Eq 4.7 represents a linear model. σ y . Characteristic “flow curve” for a bentonites. reality (see Figure 4. The constant η p is sometimes called the “plastic” or Bingham viscosity. as discussed above. Two analytical equations are usually used to characterize viscoplastic behavior: Bingham equation7 Casson equation8 & σ = σ y + ηpγ & σ 1/ 2 = σ 1/ 2 + Kγ 1/ 2 y at σ < σ y at σ < σ y [4.the transition through the yield stress appears milder. as demonstrated in Figure 4.
5 b. 60oC . Flow curve for a filled polymer melt .polyisobutylene containing 5 wt% carbon black. If viscosity at σ > σ y is constant. Ya.9] The apparent viscosity decreases when the shear rate increases. Malkin 69 Figure 4.10] .A.demonstrating gradual approach of the yield point. the behavior is not described by the Bingham equation and can be represented by the following equation: η=∞ at σ < σy η = η0 at σ > σy [4. η= σy σ = ηp + & & γ γ [4.6. as shown in Figure 4.
Such behavior is frequently called plugflow. 4. are deformed irreversibly) at σ > σ y . The plastic behavior of solids at σ > σ y is essential in such technological operations as punching of golden articles (coins and so on) or rolling of ingot steel. are regular . nevertheless. If such material is pressed through a round channel. is pressed through the hole.10 are not rheological equations of state.7 . because reactors with rotating mixing elements. where shear stress is lower than σ y .1. instead of being displaced from the rotor by centrifugal force towards the walls of a vessel. Such behavior means that the force not only acts normal to the surfaces of the discs but in the radial direction to the central axis as well. It means that there is a zone. Phenomena associated with this effect are very common in technological applications.10 If a rod is rotated inside a “rheological” liquid. they really flow (i. Another characteristic example concerns liquid between two parallel discs.7). The abovementioned and some other related observations are known under the general name of the Weissenberg effect.case 1). the inner disc is lifted up by normal force generated due to rotation (Figure 4.1 through 4. and then deform to unlimited extent when this critical stress is reached. The term “flow” has a rather peculiar meaning for such materials as metals. it is necessary to emphasize that Eqs 4.. in the central part of a channel. there is a core in the entire central zone where shear stress is very low. When the outer disc is rotated around a common axis. the rotation of the outer cylinder forces liquid into the inner cylinder (Figure 4. they only contain empirical description of experimental data obtained in unidimensional shear deformations. therefore this part of viscoplastic material does not flow but moves as a solid plug. this “strange” liquid instead of being removed from the space between the discs to the periphery of the discs. such a liquid. The term plasticity9 (and the concept of plastic behavior) is also used for solids which can be elastic (up to the yield point).3 WEISSENBERG EFFECT Weissenberg has described a set of “strange” pictures of behavior of some liquids (Figure 4. In the case of two coaxial cylinders (inner hollow). mixers of different geometry and type. In fact. In summary. and if a hole would be made in the center of one of the discs.7 .case 3). begins to wind around the rotor and climb it (Figure 4.e.7 . the stress at the axis equals zero.70 Rheological equations of state The existence of a range of low stresses in which a viscoplastic material is solidlike leads to rather peculiar properties.case 2).
A. rotating outer cylinder with liquid filling the center of a hollow cylinder (2). (Continued on the next page. Malkin 71 Figure 4. Typical phenomena usually associated with the Weissenberg effect: a rod rotating in a liquid (1).7.) . a liquid between two parallel rotating disks (3). Ya.
72 Rheological equations of state Figure 4. the last example of the Weissenberg effect shown in Figure 4. a material is mixed between two discs and pressed through a nozzle by an action of forces originated from the Weissenberg effect. the socalled screwless extruder. even though. equipment in various branches of the chemical.7. In this design. Moreover. see caption on the previous page. food and pharmaceutical industries.. Normal forces appearing due to rotation of parallel discs also give additional support in slide bearings if a “rheological” liquid is used as a lubricant. what happens at the reference point. It is interesting to understand the rheological origin of this effects. at the . The common feature of all phenomena is appearance of forces acting in the direction of shear and in the perpendicular direction. Some investigators think that the Weissenberg effect provides the ability of articulations in biological organisms and that deficiency in this phenomenon leads to an illness (“squeak in joints”).7 (case 3) was used to design a special type of machine for polymer processing.e. i. Continuation. It is equivalent to appearance of normal stresses in shear.
8. Notation of normal stresses at plane simple shear. Normal stress (diagonal component of the stress tensor) also acts.true in many real situations.) The differences of normal stresses are defined as follows: first difference of normal stresses: second difference of normal stresses: σ 1 = σ 11 − σ 22 σ 2 = σ 22 − σ 33 . (If this pressure is not very high. Ya. it will change all normal components of the stress tensor but would not influence flow. for example. It is possible to anticipate that normal components of stress tensor are related to appearance of a diagonal component in the tensor of large deformations. it is possible to neglect the compressibility of a liquid . Figure 4. The appearance of normal stresses in a simple shear is a main rheological reason for the Weissenberg effect. In order to characterize the phenomenon.A.8. it would be reasonable to suspect that only shear stress acts in a simple shear. not absolute values of normal stresses but their differences are important. Malkin 73 first sight. but undoubtedly the large elastic deformations lead to normal stresses). Their existence can be explained by large elastic deformations developed in flow (it may be argued whether this explanation is general. If. but not always. and the diagram of stresses is shown in Figure 4. This is true for many liquids. hydrostatic pressure is superimposed.
σ 2 . at least in first approximation. stress instantaneously drops to zero. though they are written in the same manner). and at high shear rate. and that is why. In all known cases.11 The left side of the diagram represents “regular” and the right side “rheological” liquids. the stepwise setting of constant shear rate leads to an immediate beginning of flow. shear stresses pass through a maximum (sometimes several maxima can be observed) before reaching the state of steady flow • after sudden cessation of flow. and this interval becomes shorter if shear rate is increased • at high shear rates. Normal stress as an effect of the second order is much smaller than shear stress at low shear rates. the normal stresses grow very quickly (proportional to squared shear rate).4 TRANSIENT DEFORMATIONS IN SHEAR (OF LIQUIDS) For regular liquids. remains constant all the time (eliminating inertial effects).11] Normal stress in shear flow is an effect of the second order. and coefficients of normal stresses are proportional to η2 .1. Figure 4. which maintains the steady flow. not σ 1 and σ 2 are used but their coefficients (analogous to the use of viscosity coefficient instead of shear stress).9 demonstrates the effect of stepwise setting of constant shear rate. σ 1 >> σ 2 . 4. .74 Rheological equations of state (σ 1 and σ 2 are not invariants of the stress tensor. there is a very prolonged time interval of slowly developing shear stresses. the initial relaxation rate increases with increasing initial shear rate. very often. shear stress decays (relaxes). The main observations for the latter are as follows: • at low shear rate. The first and the second normal stress coefficients are defined as Ψ1 = σ 11 − σ 22 σ −σ . Ψ2 = 22 2 33 2 & & γ γ [4. normal stresses become larger than shear stress. therefore they are critical for analysis of flow of some liquids (for example. After the cessation of flow. concentrated polymer solutions and melts). With shear rate increasing. In rheological literature. Shear stress. or to be more precise: (σ 11 − σ 22 ) σ 12 << 1. There are some liquids (and they are the object of rheological studies) for which development and disappearance of stresses is far from the simplest scheme. σ 1 and σ 2 are proportional to squared shear stress.
Transient behavior is also observed at other types of deformations (not only at constant shear rate). Comparison of development (at conFigure 4. Besides this complex behavior. is similar to the development and decay of shear stresses.12 This effect is illustrated in Figure 4.9. The evolution of normal stresses (regardless of σ 1 and σ 2 ). The steady flow regime is reached after a transient range of deformation.10. Development of shear stresses at preset constant shear rate for regular (a) and “rheological” (b) liquids. before the steady state and during relaxation. either in prestationary (presteady) state of deformations or during relaxation.A. then rate of deformation will be changing in time in a manner shown in Figure 4. If shear stress is set constant. when shear rate is changing due . Ya.10 for relatively low stant shear rate) and decay (after cessation of shear rate when a maximum of flow) of shear and normal stresses. stresses is not attained. Malkin 75 Figure 4. the Weissenberg effect (normal stresses at simple shear) also exists.11. The main peculiarity consists of much slower change of normal than shear stress.
i. It is thus very important to understand how different materials manifest their in .5 UNIAXIAL EXTENSION Uniaxial extension of liquids is a very important method of deformation encountered in fiber formation. the tangential stress determines behavior of a material.e.1. but the main models of the behavior are: • thixotropic (rheopectic) phenomena • viscoelastic behavior of a material. Important practical applications are numerous. For nents of deformation. Transient rheological behavior is a very characteristic time effect. From a theoretical point of view. leading to a complex relationship between stress and rate of deformation. uniaxial extension differs geometrically from deformation in shear flow. it is applicable to flow in short dies. or local hindrances in outer or inner flows. 4. The most evident manifestations of this effect can be observed at preset constant stress or shear rate.76 Rheological equations of state to a change of a relative effect of plastic and elastic components. Development of shear rate at pecially in cases when time for tranconstant stress for regular (a) and “rheological” (b) liquids. sudden changes of the diameter of a channel. In all these. example. the relationship between stresses and rates of deformation. It is therefore important to understand the reasons for these effects in different media and describe them in relation to the whole complexity of the properties of matter. esFigure 4. In shear.. it would be incorrect to characterize properties of a liquid by its flow curve alone. The reasons for the effects can vary.11. Both typical phenomena are discussed in separate Sections below. Dotted lines show sient behavior is rather long and change of elastic (1) and plastic (2) compocomparable with duration of flow. whereas in uniaxial extension only normal stresses are applied. measured only at “equilibrium” conditions (after completion of transient processes). orientational drawing. and many other cases. along with deformation rate. and formation of thin films.
In discussion of experimental data obtained for flow in uniaxial extension. Ya. For some liquids. and then normal stress and rate of deformation are measured to calculate elongational viscosity according to its rigorous definition expressed by Eq 4. If a liquid is stretched. in this case. A general picture of normal stress distribution during extension of “rheological” liquid at different rates of deformation is given in Figure 4. Eq 4. it flows (similar to shearing). The equality λ = 3η [4. which can continue for an unlimited time. corresponding to steady elongational flow with constant Trouton viscosity. and the elongational viscosity. Malkin 77 herent properties under varying conditions of loading to construct threedimensional rheological equations of state. and extension.12] For Newtonian liquids. but opposite cases also have been observed. such an obvious procedure is not applicable because the stretched material usually ruptures before a steady state is reached. λ. But at high rates of extension. there is no limiting state related to a viscous flow and stress grows with acceleration (curve 2) up to the rupture of the sample.12.13 is valid as a limiting case for any liquid. The most appropriate method of elongational viscosity measurement would be to draw a sample until a regime of steady state flow is reached. to the gradient of ve& locity. As a rule. σ E . the elongational viscosity increases at higher rates of deformation. in most cases.13] is called the Trouton law and the value λ is called the Trouton viscosity. ε (equal. increase in the rate of deformation leads to a change of their elongational viscosity. to the rate of axial deformation): λ= σE & ε [4. it must be remembered that data (as a rule) relate to the transient behavior of a material. stress reaches constant level.14 The latter case is a typical . their elongational viscosity equals 3η.12.A. At low rates of extension (curve 1). Unfortunately.13 In the range of low deformation rates. The rupture of samples at high draw ratios (factor limiting experiments in extension) is a principle difference between shearing. can be determined as a ratio of normal stress.
Drawings demonstrating characteristic modes of deformation in stretching of a regular material (a).78 Rheological equations of state Figure 4. “rheological” liquid (b) and solid (c). but “rheological” solid forms a sharp local contraction . 4.1. In “regular” liquids.13a..13: the upper drawing shows that rupture of ordinary material occurs after a continuous process of sample flow. etc.necking . water spraying. It is worth noting that rupture of “rheological” media also occurs in some different ways than ultimate breaking of regular materials.13.g. Stability of flow is of general interest in numerous applications: sailing ships. pipelines for liquid materials (water. production of plastic parts with high quality surfaces. they are pictured in Figure 4.).12. instabilities appear as a result of capillary or inertial forces. spherical droplets are formed along the stream and rupture follows. example of transient behavior and it is inappropriate to treat curve 2 in Figure 4. Regular material deforms as shown in Figure 4. flow of material in dies. The next drawing (b) relates to “rheological” liquid (e. occurs through a transition from a parent material to a neck. and so on.and following deformation. The lower drawing (c) shows rupture of stretched solids.12 as a reflection of viscosity growth in extension. Development of stresses in uniaxial extension of “rheological” liquid at low (curve 1) and high (curve 2) rates of deformation.6 INSTABILITIES AND SECONDARY FLOWS15 Figure 4. oil products. Schematically. leading to its rupture in the weakest section. The first reason leads to surface . rubber glue): during stretching. paint milling.
In some cases. It indicates that different mechanisms of instability can exist. is a dimensionless value). Turbulent flow occurs when and if the critical value of the Reynolds Number. Reynolds turbulence occurs when inertial forces exceed viscous damping of occasional disturbances. Since the critical value of the Reynolds Number reflects viscous properties of liquid. Re. Malkin 79 effects. η viscosity. which appears as a chaotic movement of liquid particles in any flow. d characteristic linear size. like any other criteria of similarity. corresponding to possible transition from laminar to turbulent flow in cylindrical channel. Then. The critical value of the Reynolds Number.14] where V is characteristic velocity. such as breaking up a stream into many droplets. Instabilities of different types accompany many technological processes. The second reason is a base of the socalled Reynolds turbulence. these new mechanisms of instability must reflect other rheological properties of material. but it is preferable to use a measure of the . and so on. waviness of fibers in spinning. E. Instabilities in flow have been observed for various “rheological” liquids and can manifest themselves in different forms.A. they are the cause of haziness of extruded films. It can be the modulus of elasticity. flow becomes unstable at values of the Reynolds Number different from that characteristic for regular liquids at the equivalent conditions of flow. unexpected effects appear. and ρ density. is about 2300 (the Reynolds Number.a primary characteristic of polymeric liquids (melts and solutions). There is a common opinion that the general reason for instability of many “rheological” liquids is their elasticity and viscoelastic effects . The concept of viscoelasticity (Chapter 7) requires us to consider at least one parameter reflecting elastic properties of material in addition to its viscosity. is exceeded. Reynolds (inertial) turbulence can also take place in the flow of nonNewtonian liquids. rough surface of cable insulation. Re is determined as Re = Vdρ η [4. For example. Ya. the main problem consists of understanding these mechanisms and correlating them with rheological properties of media. but the most interesting fact is that in the flow of “rheological” liquids.
breaking free streams. De: De = θ T [4. depending on the geometrical mode of flow and the inherent properties of a liquid. at least for dimensional reasons. called relaxation time. It is therefore reasonable to introduce a new dimensionless criterion to measure a ratio between viscous and elastic forces in flow. where T is a time factor for transient flows.16] The Weissenberg Number is close but not quite equivalent to the Deborah Number. θ. We. as θ= η E [4.80 Rheological equations of state rate of inherent rearrangement processes in a material (not specifying its nature). This time constant. the following manifestations are the most characteristic: • extrudate distortions (sometimes called “melt fracture”) • secondary flows (flows in straight channels of a simple geometrical form. such as flow between coaxial cylinders) superimposed on primary flow • interfacial and surface instabilities (boundary distortions in flow of multicomponent systems. and so on) • rheological phenomenon in inertial turbulence (Toms effect). such as the Weissenberg Number. . is defined. defined as We = Vθ d [4. Phenomena of instability in flow of “rheological” liquids can be manifested differently. However.17] where T is a characteristic time of flow.15] This value must be used as a second (additional to viscosity) characteristic property of a liquid. The value (V/d) can be treated as a characteristic time constant but it is more reasonable to use the Weissenberg number in steady flow and the Deborah Number in timedepending flows.
14 show two situations.6. right . Photographs in Figure 4.14. Ya. and as such. Instability in flow appearing in the form of regular (screwlike) defects: left .1.smooth stream in stable flow. occurs.1 Extrudate Distortions (Melt Fracture)16 Extrudate distortions are observed when polymer in the form of a concentrated solution or melt is forced through a die (orifice or capillary) and when free recovery of deformations. Besides the discussion of reasons and quantitative description of boundaries of stability (directly related to rheological properties of matter). The left picture demonstrates a stream leaving an orifice (visible at the upper part of the photograph) at low Figure 4. . Malkin 81 4. This type of instability is of special importance for polymer processing because it limits the desired tendency to increase production rate. it was treated in numerous theoretical studies.instable flow. it is an interesting general problem of continuous mechanics. stored during constrained flow in channels.A.
Instability of flow leading to disruption of a stream: transition from left to right corresponds to increase of velocity (shear rate). The right photograph demonstrates what happens to the same material when the speed of flow exceeds some limit. the instability arises as periodic oscillation. Numerous observations. During the flow inside the orifice. extrudate distortions start from slight skin defects. The shear rate was increasing from left to right. speed.82 Rheological equations of state Figure 4. Then they are enlarged to regular surface defects (sometimes called “sharkskin”). similar to those presented in Figures 4.15 show more severe consequences of flow instability. .14 and 4. and when the polymer melt was released from a die (capillary or orifice) at high velocity. the stream disintegrated. The flow is stable and the surface of the stream is quite smooth. large inherent forces (or energy) were stored in the material. In this case. as a rule. The regular defects resembling a screw appear on the surface as a manifestation of instability. fragmenting into separate elements. show that. The photographs show frozen samples of streams leaving a die.15.15. Photographs in Figure 4.
Malkin 83 forming gross regular variations of a crosssectional area and shape (sometimes looking like a helical screw on extrudate) which can be an evident result of a “stickslip” mechanism. It is therefore necessary to find an explanation of this effect other than the Reynolds turbulence. because viscosity of a melt is very high. Finally. This is the reason why “liquid” begins to behave. but similar to a solid. is unstable and movement of markers is chaotic. rubberlike material which does not flow but slides as a plug along a channel. It is direct evidence of flow instability. The appearance of gross distortions of periodic or aperiodic types in the flow of polymers (melts and concentrated solutions) can be accompanied by an abrupt jump of the flow rate .18 Perhaps the scatter of these values can be explained by difficulties in determination of an exact moment when flow instability occurs and/or by difficulties in distinguishing between different mechanisms leading to similar fea .A. as documented in Figure 4. Gross extrudate distortions such as melt fracture are related to a nonlinear phenomenon such as phase (or relaxation) transition. and (most important) the effect under discussion does not correlate with any definite value of the Reynolds Number. illustrating the meaning of “melt fracture”.17 This effect is explained by loss of fluidity and sliding along a solid wall. sometimes as low as 105. Ya. The exact value of the Weissenberg Number depends on details of the method used for its estimation. surface distortions occur as a consequence of nonlinear effects in deformation of “rheological” liquids .during flow through a capillary (die) under constant pressure. There are at least two causes for extrudate distortions. At relatively low flow rates. not like a fluid. one can find critical values of the Weissenberg Number in shear flows in the range from 1 to 10. namely about 5. when alternating rough and smooth zones appear on the surface of an extrudate. The main result of numerous experiments shows that instability in flow in the form of “extrudate distortion” occurs at very low values of the Reynolds Number. due to relaxation transition of a linear polymer into a rubbery state.such phenomena as their elasticity and/or normal stress in shear flow. the instability of this type reaches a form of chaotic distortions and ruptures of stream.“spurt” . Many direct observations of flow lines (made by markers suspended in a flowing liquid through transparent walls of a channel) showed that movement of a liquid inside a channel at high velocities. In original publications. The meltfracture instability appears at some critical value of the Weissenberg Number.15. when an extrudate becomes irregular.
4. Indeed. meaning that the energy consumption in transportation of “rheological” liquids is increased in comparison to a regular liquid of the same viscosity. The most wellknown case of secondary flow in Couette flow is called Taylor instability. etc. and a secondary flow forms closed flow lines. the main flow takes place in a circular direction. strong nonlinear effects and phase (relaxation) transition in flow can superimpose and therefore lead to somewhat deceiving conclusions concerning quantitative criterion of instability. On increasing the flow rate.16 along with some other cases of secondary flows. It is equivalent to the motion of coaxial cylinders with radii much larger than the gap between the cylinders.19 It is shown in Figure 4. and the curvature effect is neglected. extrusion.16a). Extrudate distortion is velocity dependent. If a liquid is placed in a gap between two coaxial cylinders. Secondary flow does not appear in “rheological liquids” in channels having a circular crosssection but can be found in channels with crosssections of other geometrical forms. . Extrudate distortion has an industrial importance because it limits the increase in flow rate.84 Rheological equations of state tures of unstable flow. For example. the secondary flow causes much stronger instability. called Taylor cells (Figure 4. A quite equivalent situation occurs in the flow between two parallel plates driven by the motion parallel to the plates. This case is known as plane Couette flow. output in many technological applications such as fiber spinning. and thus. and that is why they are so closely related to such gross effects as flow distortions. secondary flow in a straight cylindrical channel produces circular flow lines in planes perpendicular to the axis of a channel.2 Secondary Flow The initial stage of instability occurs due to the socalled secondary flow. are shown in Figure 4. Secondary flows (closed vortices). Secondary flow increases resistance to flow.1. Secondary flow is formation of closed vortices in planes perpendicular to the direction of the main (primary) flow. based on laboratory data.16b. and begins beyond some limiting velocity of flow. governed by the movement of solid boundaries in a liquid sample. The understanding of the principles and controlling rheological parameters allows one to evaluate the processability of materials and select them. observed in the flow of a “rheological’ liquid in a gap between a cone and a plate when a cone is rotated around its axis. and one of them is rotated.6.
Taylor instability occurs in any Newtonian liquid if a critical value of the Reynolds Number is exceeded. Instability of the Taylor vortices is explained for regular Newtonian liquids as a result of inertial effects (analogous to the Reynolds turbulence).16c). If a liquid is forced to flow through a straight channel with an elliptical or rectangular crosssection in the direction of the main flow along the axis of a channel.16d). T. calculated as . Secondary flows in different channels: between two rotating coaxial cylinders (a). Malkin 85 Figure 4. Ya. occurs in a “rheological” liquid flow through a sudden narrowing (Figure 4. The most spectacular secondary flow. near a sudden change of crosssection surface area (d). along a nonround element (b). in the form of closed vortices. the secondary flow forms closed flow lines in the crosssection of a channel (Figure 4. Theoretical analysis of the flow of a Newtonian liquid shows that the stability threshold for flow between two coaxial cylinders is determined by the value of the Taylor Number.16. in channel crosssection (c).A.
Experiments show that elasticity (for example. The height of the Taylor cells formed in a Newtonian liquid in a section along the axis of cylinders is roughly equal to the width of a gap. for example.18] Ω i and Ω o are the rates of rotation of the inner and outer cylinders. as documented. Secondly. Firstly. cells can be of very irregular form. if Ω o = 0. Instabilities observed in highly elastic (rubbery) liquids are quite different than those described for Newtonian or weakly elastic liquids.19] is the Reynolds Number determined for a circular flow between coaxial cylinders. the form of cells is close to square. quite analogous to instability of the melt fracture type which also appears irrespective of the Reynolds Number and even at Re close to zero). instability occurs irrespective of the Taylor Number (for example. Elasticity of “rheological” liquids strongly influences the stability of flow. b = 1. i. wavy cells with boundaries periodically changing with time. again reminding us of periodic distortions of an extrudate. . it can happen even at T close to zero. Thirdly. reminding us of rough extrudate disturbances in capillary flow. some investigators observe new types of instability in the Couette flow.e. depends on rheological properties of a liquid. Besides. respectively. characterized by the normal stresses) can stabilize the Couette flow. it is possible to observe instability of the oscillatory type.86 Rheological equations of state T =2b(Re)2ε where b= Ωo −Ωi Ωi [4.20 Appearance of cells of different type.. ε = δ R i is the ratio of the gap to the radius of the inner cylinder and Re = Ω i R i δρ η [4. One of the main theoretical findings for a Newtonian liquid is the existence of the minimal value of the critical Taylor Number equal to 3390 (at b = 1).
It does not happen immediately after the beginning of rotation. In circular flow of a “rheological” liquid. creating a combination of instability of secondary and extensional flow. in a typical case. In particular. for example. as shown in Fig. It superimposes on vortex formation. the draw ratio increases.A. and a result of .17.e. It is interesting to emphasize that these transitions in behavior of vortices correspond to the character of flow inside a die and distortions of an extrudate. flow ruptures in a continuum media. Inertial instability in a form of closed vortices appears in circular flow of a Newtonian liquid between a cone and a plate at sufficiently high values of the Reynolds Number.16b.5o. Thus the observations regard the transition from typical secondary flow to a chaotic instability of turbulent type. However. With increasing flow rate. More severe effects cause a rupture of a liquid sheared between a cone and a plate. in liquid transportation or in a die in industrial extruders or capillary viscometers.. This situation is typical in a transition from one diameter of a pipe to a smaller diameter. Many visual experiments demonstrated that vortices appear at the corners. Another interesting feature of flow through sudden decrease in crosssection surface area is axial extension of a liquid near the axis of a stream. at low flow rate. Malkin 87 Instability related to a secondary flow also can be observed in other circular (rotational) devices. The coneandplate system is very often used in experimental rheology for viscosity and normal stress measurement. fracture of flow lines is observable along the axis.16d). This effect also can be considered as analogous to flow disturbances and melt fracture of an extrudate leaving a die. A very important type of secondary flow occurs when there is a sudden narrowing in axisymmetrical geometry of a channel (Figure 4. i. instability begins from distortion of a meniscus due to elastic effects. Experiments proved that the shape and behavior of such vortices are characteristic for properties of a “rheological” liquid. when a rate of extension exceeds some threshold value. regular pulsation of vortices occurs. and in this case the angle between a cone and a plate does not exceed 4 . Further increase in flow rate causes pulsations to become irregular. 4. Ya. as is shown in Figure 4. Increasing the rate of flow (equivalent to the increase in the Weissenberg Number). the stable vortices exist at the corners. This phenomenon is a limiting case of instability in extensional flow. These distortions can be rather extensive. but after a period of deformation.
17. these effects leads to extrudate distortion and melt fracture.88 Rheological equations of state Figure 4. in shear curvilinear flows. for example. The first type is related to normal stress influencing critical conditions responsible for secondary flows. Photograph illustrating the appearance of closed vortices near a sharp corner around a sudden reduction of crosssection surface area. as mentioned before. In summary. . with all the technological significance of these effects for processing of viscoelastic materials. in gaps between two coaxial cylinders. a cone and a plate. in threedimensional flows in sudden change of crosssection. instabilities of different types occur.
21 observed in mixtures and solutions. the following phenomena are met which can cause instabilities of different type.1. as explained in the classical works by Rayleigh). Malkin 89 causing formation of regular vortices (this is a weak nonlinear effect). the secondary flow appears as a chaotic movement of particles in a liquid or irregular distortion of smooth surfaces of a stream. very diluted water solutions of some .22 It is impossible to avoid occasional small fluctuations in fiber diameter. The second type causes severe distortion of a media in oscillatorytype movement (this can be treated as a strong nonlinear effect). That is why “rheological” liquids. but instability is the phenomenon which increases these fluctuations. As mentioned in discussion of extensional flow of “rheological” liquids. Draw resonance is a wavy periodic change in stream (fiber) diameter occurring at constant feed (takeup) rate. Ya. The irregular instability which occurs as a result of ruptures in a continuum media can be considered as a result of phase (or relaxational) transitions. for example. a stream is initially converted to a series of elongated droplets connected by threads. Jet breaking occurs in a Newtonian liquid due to surface tension (capillary waves break up a stream. such as the commercial process of fiber spinning and orientation.6.3 Waving in Extensional Flows There are very interesting and unusual effects observed during stretching of “rheological” liquids. and this phenomenon can be described in terms of nonNewtonian behavior in uniaxial extension. leading to stream stabilization. These effects are important in many technological processes. It is reasonable to assume that draw resonance is due to elastic behavior of a liquid. In practice. The effect close to it is a phase separation which occurs due to shearing. where the natural tendency to increase the process rate is contrary to the requirements to prevent process instability caused by “fast” flow. In this case. Draw resonance affects quality of fibers (expected to have uniform crosssection). thus the Deborah Number is the determining parameter for this phenomenon. These threads can be stretched at a rather large ratio (especially if the resistance to stretching increases on drawing).24 The main difference between a regular and “rheological” liquid is in the form of a jet before breakup. and can be treated as a “phase” nonlinear effect.A. 4.23 The reason for jet breaking is a growth of small occasional wavy variations in a diameter of a jet until a cylindrical jet breaks up into droplets.
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polymeric substances, can be successfully used in fire extinguishing when it is desirable to prevent jet breaking and to increase the distance of stream delivery. Necking was already mentioned in discussion of uniaxial tension of solid viscoelastic materials. It is an abrupt deviation from uniform (homogeneous) deformation.25 It is an instability of the phase type, consisting of selfsustaining change in the diameter of a stretched filament. This effect is typical for large deformations of solid materials. It is related to relaxation or phase (recrystallization) phenomena. It also occurs during extension of liquids (polymer melts). Necking is very important in such technological operations as orientation of amorphous materials and orientational crystallization in fiber spinning. Rupture of a stream, observed in uniaxial extensional flows, is the final stage of instabilities. It can happen as a result of development of surface waviness in draw resonance or jet breakup (surface instability) or as a result of cohesive fracture even though it is encountered in liquids. It is important to mention that this cohesive fracture occurs at the same magnitude of stress as in melt fracture of an extrudate leaving a die. It emphasizes the correlation between the strength (rupture) of a material and major distortion observed in concentrated solutions of polymers and melts.
4.1.6.4 Interfacial and Surface Instability
In coating processes, shear flows of films with a free surface are observed. A technologist expects that a liquid film on a solid base should be smooth and homogeneous  not always the case because of surface instabilities in a flow of a coating liquid.26 It is important in surface coating, especially in automotive application where anticorrosive coatings are used. The model of such a situation is a flow of a liquid film along an inclined plate. A stream with a free surface can become unstable, as demonstrated by imperfections of a free surface. An analogous phenomenon is observed in multicomponent flow through channels. Waves are formed at the boundaries of two liquids. Interfacial and surface instabilities occur for Newtonian liquids due to inertial effects. The stability of flow is controlled by the Reynolds Number and the surface tension. The influence of the Weissenberg Number, controlling surface instability, is an additional factor typical of “rheological” liquids. Theory predicts
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that elasticity of liquid, even at very low values of the Reynolds Number, can lead to waviness of a surface, which is a purely rheological effect.
4.1.6.5 Rheological Phenomenon in Inertial Turbulence (Toms Effect)
Inertial turbulence exists in “rheological” liquids similar to many other effects of instability discussed above. Also in this case, special properties of some “rheological” liquids lead to a very abnormal (compared with regular liquids) phenomenon known as the Toms effect.27 It is a very interesting, unusual, and important phenomenon worthy of separate discussion. In order to understand the meaning of the Toms effect, it is necessary to repeat some fundamental concepts of classical hydrodynamics of viscous (Newtonian) liquids. It is wellknown (see also Chapter 5) that pressure drops during the flow of viscous liquid through a cylindrical tube (capillary, channel), i.e., the difference of hydrostatic pressures at the ends of a tube, ∆P, is related to the volumetric flow rate, Q. If and until the flow rate is not very high, the relationship between these two main macrocharacteristics of a stream is expressed by the Hagen Poiseuille equation,28 which can be written as follows ∆P = 128ηLQ πD 4 [4.20]
where D is a diameter of a tube, L length, η viscosity. Alternative form of Eq 4.20, when substituting the volumetric flow rate by an average velocity, V, is as follows: Q= 1 πD 2 V 4
Then we have ∆P = 32ηLV D2 [4.21]
Finally, let us introduce dimensionless characteristics of flow, i.e., the Reynolds Number, defined in Eq 4.14, with V in this formula being an average
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Rheological equations of state
velocity. The second dimensionless number is a coefficient of friction, λ, which is determined as λ= ∆P D 1 L ρV 2 2 [4.22]
Now, the Hagen  Poiseuille equation can be written with dimensional variables λ= 64 Re [4.23]
Sometimes both numbers λ and Re are determined, not through diameter, D, but by radius, R, of a tube, then Re R = VRρ ∆P R ; λR = 1 η L ρV 2 2
So the Hagen  Poiseuille equation looks like this: λR = 16 Re R
Changing D for R does not influence the result, and both dimensionless forms are equivalent to the initial Eq 4.20. Application of dimensionless Numbers λ and Re is of general meaning for hydrodynamics flow through tubes, because such an approach allows one to generalize data for different liquids and tubes of various geometrical sizes (diameter and length) by representing them in dimensionless coordinates λ and Re in one relationship. It is generally accepted to analyze the pressure versus output (flow rate) relationship in terms of λ and Re for any flow velocity, not only when Eq 4.20 is fulfilled. It is well known that the Hagen  Poiseuille equation corresponds to the experimental data only up to some critical value of the Reynolds Number, Re*, which is close to 2300 (i.e., log Re* = 3.36). Increasing flow rate (or the Reynolds Num
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ber), the transient regime is attained, which lies in the range of Re* to Re**, and at Re >Re**, turbulent flow occurs. The dependence of the friction coefficient on the Reynolds Number, for a fully developed turbulent regime of flow, in the range of the Re values up to 105, is well described by the empirical Blazius equation29 λ= 0.3164 Re 0.25 [4.24]
The generalized λ(Re) dependence, established on the basis of numerous research experiments covering all regimes of flow, is drawn in Figure 4.18. In this graph, constructed in log  log coordinates, the line P corresponds to the Hagen Poiseuille equation, and the line B is drawn according to the Blazius equation. Evidently, the transition from laminar to turbulent flow results in a great increase of resistance to flow, with corresponding increase of energy due to the movement of a liquid. The critical values of the Reynolds Numbers Re* and Re** are also marked in Figure 4.18.
Figure 4.18. General view of the dependence of friction coefficient on the Reynolds Number. t  regular (Newtonian) liquid,  “rheological” liquid, P  Hagen  Poiseuille equation, B  Blazius equation, V  Virk asymptote.
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The Toms effect in “rheological” liquids describes the decrease in resistance to flow (drag reduction) in adding very small amounts of some components to a regular liquid (the latter can be, for example, water or oil). These special additives are, as a rule, polymers of very high molecular weight (with very long flexible chain) and their concentration in solution can be as small as 1  100 ppm (parts of an additive per 1 million parts of a liquid). These microquantities of additives are the reason for the appearance of new rheological properties of matter. The effect appears from some threshold value of Re, marked in Figure 4.18 as Re*. Black points in Figure 4.18 correspond to a pure liquid (solvent) and the light points to “rheological” liquid (very dilute polymer solution). In the laminar and transitional ranges, both sets of points fall into the same dependence. The same is true at the beginning of a turbulent regime of flow, but at Re > Re* the situation changes radically and a coefficient of friction for a “rheological” liquid becomes lower than for regular liquid. Many publications have been devoted to the Toms effect. The main results about general peculiarities of the Toms effect are: • the value of Re* decreases on increase of solution concentration; in the limiting case, Re* can become as low as Re**, and the transient regime of flow between Re* and Re** disappears • the degree of drag reduction depends on the material properties (type of liquid and an additive, concentration of a solution, and so on), i.e., the effect depends on rheological properties of a liquid • there is a limiting (asymptotic) degree of drag reduction in polymer solutions, common for all materials; it can be represented by dimensionless variables as described by the equation called the Virk asymptote:30 λ = 2.36Re 0.58 [4.25]
The Virk asymptote is draw in Figure 4.18 under the symbol V. Comparison of graphs B and V in Figure 4.18 shows that the maximal effect of drag reduction can reach 75%. Certainly, it is a very strong effect, and as such, it finds practical applications in liquid transportation. Also, special additives are used as a smoothing agents of fast movement of ships when turbulence requires additional energy use. The additives, by decreasing resistance, promote attaining higher speeds at the same engine power.
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4.1.7 THIXOTROPY AND RHEOPEXY
Very often, real materials change their properties with time due to the structure transformations resulting from an action of external forces or rebuilding their initial structure at rest. The reason for change can be a preliminary deformation: in this case, rheological properties (in the simplest case  viscosity) change along with deformation and continue to change at rest after cessation of deformation. Such phenomena do not exist in Newtonian liquids having constant viscosity. The change of properties can be fully reversible, though it may require a long time or even special actions (for example increase of temperature to accelerate processes during the material’s rest). Some changes initiated by deformation can be stored in a material and then recovery may be incomplete. Both cases are real and observed; for example, in yogurt on mixing, in preparation of rubber compounds, shearing of thickened greases, pouring building materials, and so on. If viscosity decreases during mixing and returns to the initial level on rest after shearing, such a phenomenon is called thixotropy.31 The reverse phenomenon is called rheopexy. The definitions of thixotropy and rheopexy are valid not only for regimes of steady flow but also for transient deformations. The use of these terms is not always very definite, and thixotropic and rheopectic effects are frequently mixed with other viscoelastic effects. A typical example of thixotropic behavior of liquid is given in Figure 4.18, showing the relationship of viscosity versus shear rate. The upper part of a curve was measured on increasing shear rate; on reverse measurement (shear rate decreasFigure 4.19. Hysteresis loop in continuing from maximum to minimum), ous change of shear rate formed due to thixotropic properties of a liquid. An arviscosity is lower than on ascending shear row shows the direction of changes of exrate change. The lower part of the curve perimental conditions in viscosity measurement. represents viscosity of a medium with
and that is why thixotropic effects are more common than rheopexy. for example. as was investigated in fundamental works by Tobolsky. kinetics of physical or chemical processes in a material related to the effect of stress. In this sense. Certainly this type of phenomena is especially important in applications of polymer technology (synthesis and processing). the latter being a very special case in materials with some kind of unusual intermolecular interactions. Results also depend on the conditions of measurements of these properties. Deformation of moist sand or concrete are typical examples of dilatancy.34 The second case regards chemical reactions of polymerization. This phenomenon is particularly important for rubbers.35 All these chemical reactions result in considerable changes of rheological properties (not only viscosity) of a material. and chemical transformations in polymeric chains. One of them is a change of stresses (relaxation) in deformed materials as a result of chemical reaction initiated by stress. particles must be separated and liquid acts as a lubricant.96 Rheological equations of state structure changed by previous deformation. thixotropy is a consequence of structure rupture and rheopexy of structure buildup. for example. Changes in the matter structure are followed by changes in its properties. Structural effects in highly filled liquids can lead to a very peculiar rheological phenomenon called dilatancy. They lead to new values of parameters characterizing these properties. viscosity of a liquid or modulus of elasticity of a solid. The set of these parameters differs for any actual state of a material structure. Mixture becomes dry under pressure but recovers and becomes moist after the pressure is removed. a new class of phenomena is discussed within the frame of rheology. strong ionic interaction or hydrogen bonding. curing of oligomers.32 Solid particles in such materials are in a state of close packing. There are two main cases of chemorheological effects. Kinetic effects in rheological systems can be called rheokinetics or chemorheology.33 The change of rheological properties on deformation and rest reflects the structural rearrangement caused by application of external forces. which is volume increase caused by shear. it . Particle coating by liquid increases volume. It can be expected that external forces more likely promote rupture rather than a buildup of structure. Under shear.19. Measurements are used to characterize thixotropic properties of material and their quantitative measure is an area of a hysteresis loop between two curves in Figure 4. From this description. It is important to emphasize that in both cases. that is.
and colloid systems (for example. and the effects are caused by transformations of a physical structure of matter. If one expands the function σ = f(ε ) into a power series. Ya. 4. In discussion of nonNewtonian flow. Sometimes large elastic deformations are treated as a secondorder effect. the quadratic member is negligible. it already has been mentioned that the idea of physical nonlinearity. Malkin 97 is apparent that the behavior of material is nonlinear. higher members of the series are negligible in comparison with the linear members. That is why rheological effects related to structural transformations of a material can be called physical nonlinearity of rheological behavior. but as ε approaches 1 and exceeds it. The properties become more complex for materials which can withstand large deformations (ε > 1). some polymer solutions. as a reason for this effect. Thus. properties of some materials are better described by power law: σ E = Kε m where K and m are empirical constants (m is not equal to 1). A similar reason can lead to other rheological effects. because at ε << 1 and at n > 1. was introduced by Ostwald1 under the name of structure viscosity.8 NONLINEAR ELASTICITY According to the Hooke Law the dependence of elastic deformations on stress is linear and the modulus of elasticity (the ratio of stress and deformation) is a material constant. the Hooke Law appears not exactly true. while Hooke dealt with rather simple homogeneous materials. can be expanded into a power series. the ε n << ε . at rather low deformations. the dependence σ(ε ) is nonlinear and. This is a case especially important for rubbers. Even for some ordinary materials. such as σ = f(ε ). The first (linear) member will always be dominating. When ε << 1. then the “secondorder” effect becomes dominant. This idea looks quite natural because any complicated function. approximately at the same time when Hooke formulated his Law. then the term “large elastic deformations” means that the second (quadratic) member of a series becomes comparable to the linear member. It is worth mentioning that Bernoulli conducted his experiments with biological materials which are rather complicated in their structure. dispersions of aluminum .1.A. as demonstrated by Bernoulli.
(drawing force divided by initial crosssection of a sample) is used instead of the true stress. and the Young modulus equals 3G ∞ . within the limit of small deformations.36. Draw ratio. the socalled KuhnGuthMark equation. The divergence from linearity of σ(ε ) dependence.26 takes the following form σ o = G ∞ (λ − λ2 ) [4.98 Rheological equations of state naphthenates). the Hooke Law is valid.28.37 can be written (for uniaxial extension) as σ E = G ∞ (λ2 − λ1 ) [4.1). is illustrated in Figure 4. It is important to emphasize that Eq 4.27] It is easy to show that within the limit of small deformations (at draw ratio λ → 1or ε << 1). (force divided by a current crosssection of a sample. predicted by Eq 4. Another singleconstant equation for large defor . the nonlinearity of stress versus deformation dependence is evident as a typical rheological effect. There are some popular equations for describing dependence of draw ratio on the stress of rubbers.26 becomes σ E = 3G ∞ ε [4. λ.28] It means that.20) equals 3(λ . If the volume of a sample does not change during deformation (very close to reality for rubbers). σ. and λ draw ratio. the relationship between conventional and true stresses is very simple σ o = σ Eλ and Eq 4. Eq 4.20. The most often used formula. Sometimes “conventional” stress. taking into account changes of the crosssection along drawing).26] where G ∞ is an equilibrium modulus. It is quite evident that nonlinear effects appear at rather large deformations. In such cases. corresponding to Eq 4. for these materials can reach values of an order of 10 and even more. Initial slope of the curve (dotted line in Figure 4.26.26 is a singleconstant equation (contains only one parameter G ∞ ). σ o .
experimental data on uniaxial extension at large deformations (like any other set of experimental data) can be described in many different ways by means of equations of various mathematical structure. Dotted line is linear stress versus deformation dependence.20.38 For uniaxial extension it has the following form σ E = A(λ − λ 1 2 ) where A is an empirical constant. Quite different twoparameter equation of power type. There are some other inevitable limitations for use of arbitrary stress versus deformation equations and they will be discussed below on the basis of general principles for constructing rheological equations of state.29] Figure 4. Eq 4. Malkin 99 mation was proposed by Bartenev and Khazanovitch. Ya. discussed in scientific literature and used in practice. Certainly.30 is close to the equation earlier discussed by Ogden41 and can be treated as an analogue to the power law for nonNewtonian liquids (Eq 4. Among them is the Mooney . this equation is written in the following form σ E = 2[C1 (λ2 − λ1 ) + C 2 (λ − λ2 )] [4. was proposed.40 For uniaxial extension it has the following form: [4.30] σ E = 2B(λn \ λ \n 2 ) where B and n are empirical constants. where C1 and C2 are empirical <%5>constants (parameters). Numerous other equations for large deformations. Stress versus deformation dependence predicted by the KuhnGuthMark equation. That is why . For uniaxial extension.A.39 which is the most popular equation. for large deformations.5). are multiparametric. It seems that there is only one formal limitation: existence of a linear region in the limit of small deformations.Rivlin equation.
43 is also related to large elastic deformations developed during the flow through a channel. they correspond to nonNewtonian flow of “elastic” (i. repeated deformations (stretching .e. when large deformations destroy the inherent structure of a material. for example. for example. When an elastic liquid leaves a capillary (or a die). In this case. For example. though a diameter of stream in flow of classic Newtonian liquid must decrease. at least in some cases. The origin of this effect. It is interesting to mention that. according to original experimental data. Large elastic deformations lead to numerous macroeffects and they can be a source of some effects which might be treated as independent rheological effects. and perhaps. it was shown that some nonlinear effects may occur purely for geometrical reasons and can be explained and described if we want to use “correct” (or corrected) measures of the effect.45 In discussion of the theory of deformations (Chapter 3). It leads to an increase of its length. There are some direct consequences of large elastic deformations in different media. For solids. That is why the Poynting effect and some other related manifestations of large elastic deformations are sometimes called effects of the second order. The phenomenon is called the Mullins effect. called die swelling or the Barus effect. This situation is typical. One of the most interesting cases includes superposition of large elastic deformations and thixotropy..compression cycle or periodic large amplitude shearing) lead to change of observed stress versus deformation dependence which approach some “equilibrium” shape only after several loadingunloading cycles. axial deformations observed in the Poynting effect are proportional to the squared angle of twisting.44 Large elastic deformations can act in combination with other rheological effects. it includes the socalled Poynting effect. its diameter increases above a diameter of a channel. for filled rubbers (rubbers containing reinforcing filler such as carbon black) or crystalline solid plastics. capable of superposition of flow and recoverable deformations) liquids. large elastic deformations during shear are intimately related to the Weissenberg effect.100 Rheological equations of state other possibilities for describing large deformation will be discussed below within the frame of a general theory of elastic bodies (Chapter 6). An increase of a diameter (swelling) of liquid streams is another manifestation of large elastic deformations.42 It consists of extension of a body when sheared. even though in a classical Hookean solid the deformation of one type (twisting) must not influence deformation of another (longitudinal extension). introduction of Hencky’s measure of deformations allows .
though viscoelastic behavior of a material can be observed in numerous other experiments and applied situations. We can distinguish three different cases: • limited creep . called creep. This phenomenon is called viscoelasticity. That is why corresponding phenomena. very slow deformations of metals under stress. even such as metals and stones. minutes. Creep is slow development of deformations at a constant stress. is illustrated in Figure 4. the most important class of materials possessing viscoelastic properties include polymers (rubbers. The idea of viscoelasticity of solids was introduced into scientific discussions by Lord Kelvin (W. application of constant stress leads to flow with a constant rate of deformation. on the one hand. It can be observed in deformation of all materials. can be treated as geometrical nonlinearity in rheological behavior. There are two main phenomena related to viscoelastic properties of a material. who applied this concept to deformation of the Earth. They are creep and relaxation. The behavior. plastics.21. and many other phenomena of this type are all consequences of viscoelastic properties of real materials. 4.1. which are only due to geometrical transformations of a body and can be excluded by introducing “proper” quantitative measures of an effect. For a Hookean elastic body. application of a constant stress creates constant deformation.46 Longterm. this behavior reflects viscoelastic properties of solids . Malkin 101 one to “linearize” the behavior of a material because deformations are summarized in accordance with a linear rule. solutions) because viscoelastic phenomena are observed in deformations of these materials in ordinary timescale (seconds. The difference is only in the relative participation of elastic and plastic components and the sensitivity of the method used for their investigation.9 VISCOELASTIC BEHAVIOR (TIME EFFECTS AND SUPERPOSITION OF FLOW AND ELASTIC DEFORMATIONS) Superposition of viscous and elastic behavior is a typical and important rheological effect characteristic of real materials. For a Newtonian liquid. which appears (practically) instantaneously and does not change as long as stress continues to be constant. on the other. while observation of viscoelastic effects for other materials requires either very short (fraction of a second) or very long (years) timescales.47 However. Ya.deformation reaches its maximum level and after that does not change. Thomson).A. and hours). damping of vibrations of bells. and water and oil.
after a transient period. after the dotted line xx. pipes under internal pressure. for example. It means that after removal of an external force. This difference is demonstrated in Figure 4.21. this situation is typical for both liquids and solids.102 Rheological equations of state • limited rate of deformation . for hightemperature steels used in gas turbines. the initial dimensions of a body are only partially be restored. if stresses are sufficiently high and exceed cohesive strength of material. second case). Creep is of special importance in different types of plastics. ited deformation (curve 1). Creep is an important property of many materials which are not very “rigid” or/and fragile.21 gives similar picture as the (curve 3). Creep is also important for parts working under high stresses for a long time.21. the resulting deformation is zero in the first Figure 4. as characteristic. the behavior reflects viscoelastic properties of liquids which flow at constant rate of deformation • accelerated creep .not only deformation but also the rate of deformation show limitless increase until the rupture of a body. constant rate of deformation is set. including reinforced plastics. full deformation consists of elastic (reversible) and plastic (irreversible) components. which can be treated as a continuation of first two curves in Figure 4.22. and accelerated creep Figure 4. In the first case shown in Figure 4.21. in the second case (the third case in curve (curve 2). highly filled . full deformation is completely elastic (or reversible). for example. The portions of curves. the initial dimensions of a body are completely restored. if an external force is removed. It means that. Different types of creep: limcase and there is a residual deformation. In two other cases. Creep is practically nonexisting in metals at room temperature but it becomes a very serious problem if a metal is used close to its melting temperature. reflect behavior of a material after removal of an external force.marked at the ε f . This constant value of deformation rate is given by the curve 2. limited constant rate of deformation .
as illustrated in Figure 4. it is necessary to introduce stress equals σ ∞ . In real bodies. who introduced an idea of relaxation in physics. Relaxation is a slow decay of stresses at constant deformation. For a Newtonian liquid.23: • stress may dissipate and completely disappear . In fact. Malkin 103 polymers (for example. εf . moval of stress for a viscoelastic solid body with residual deformation. Thus. can be stored in a material for unlimited time. in the case of a viscoelastic solid. One can distinguish two possible situations. time as a factor determining the stress versus deformation relationship and accept that an unambiguous correlation between stress and deformation does not exist. because the derivative of a constant is zero). solid propellants). mation is absent (it is absent at constant deformation. Maxwell.23. (curve 1) and viscoelastic stress cannot act if rate of deforliquid (curve 2). Relaxation in sidered as a mutual delay in change of stress and viscoelastic liquids (curve 1) and solids (curve 2). For a Hookean body.23. the concept of relaxation is much wider than only slow decay of stresses. stress decay is not instantaneous but requires time as shown in Figure 4. That is why measurement of creep is very popular in polymer material science. Elastic recovery of deformation after retion. stress continues to remain constant during preservation of deformaFigure 4. Ya. because they are used at temperatures not far below their melting temperature. Both basic viscoelastic phenomena can be conFigure 4. σ ∞ .A.48 used this term to designate delayed restoration of a molecular structure of matter dis . Residual deformation.22.this is a case of stress relaxation in a viscoelastic liquid • part of an initial stress.
A rather obvious example of relaxation is offered by damping of vibrations by shockabsorbers in cars and other transport devices. At least in some cases. In this line of thought. ovals.. In practical applications. the viscoelastic behavior can be treated as a thixotropic effect of some kind.1.10 FLOW AROUND SOLID OBSTACLES Flow of liquid around a solid body (obstacle) is an interesting and important example from hydrodynamics. relaxation is always considered when a material or a structure as a whole is deformed. seals can be very tightly pressed by screws.e. viscoelasticity is considered as an independent phenomenon and the theory of this effect (Chapter 7 is devoted to the complete discussion of this theory) is constructed regardless of analysis of structural and/or kinetic processes which may take place in a body. similar to river flow under the bridge or a ship moving in a sea. Eiffel in the 19th century) showed that the general hydrodynamic picture can be demonstrated as in Figure 4. Any time effect is a consequence of various transformations of inherent structure of a material and kinetic processes of this restoration. as a general rule. and so on). they appear even in laminar flow and remain stable after passing a solid body in the form of socalled Karman’s strip. However. cylinders. both phenomena are intimately related to each other. a material becomes unstressed and sealing becomes not as tight as it was in the beginning. disturbed for any reason. In initial state. deformation of a seal continues to be constant) but due to relaxation. β* • formation of vortices after passing the point of first contact between a body and a stream. Classical experimental and theoretical investigations (initiated by A. the hydrodynamic resistance to movement is of interest.24. and there are two characteristic effects observed: • existence of a point at which a stream is diverted by a body. These effects are observed in flow around any solid body with smooth curvature (spheres. In both situations. The effect is the same when a stream flows around a solid body or a body moves through a liquid medium. Exploitation of seals in pressure vessels is another example.104 Rheological equations of state torted by any external factor or (maybe) simply by a statistical fluctuation. It is worth mentioning that the hydro . 4. Then we can understand relaxation as restoration of an equilibrium state. The relative positions of a cover and a vessel are not changed during work (i. and this point is characterized by the value of an azimuthal angle.
A. β*. The picture observed when a liquid flows around a solid body at transient range of the Reynolds nificance in the design of heat Numbers between laminar and turbulent regions. Treating this phenomenon as a rheological effect (though one may think that there is some conditionality in such treatment) has the following reasons: • it happens with materials which manifest many other rheological effects discussed above . elasticity of a liquid. and contribution of viscous friction does not exceed 2% of the total resistance. Experiments and some theoretical studies showed that the azimuthal angle. namely.11 PHASE TRANSITIONS INDUCED BY DEFORMATIONS Deformations of some materials can lead to phase (or at least to relaxation) transition under isothermal conditions. found in flow of numerous Newtonian liquids is rather constant and close to 82o in the range of the Reynolds Number from 3×102 to 3×105. Ya. The shift can be so large that β* reaches 180o and flow approaches an undisturbed pattern flowing around a body in the range of the Reynolds Numbers mentioned above. Malkin 105 dynamic resistance in all cases is primarily determined by the pressure of a stream before the point of contact. Heat and mass exchange processes between a liquid and a solid body during these process is of special sigFigure 4. 4. etc. A more pronounced effect is observed if liquid is not purely viscous but also has elastic properties (for example. It is important to emphasize that the value of the azimuthal angle. some biological liquids. is lower than 82o for nonNewtonian liquids. typical of real technological application. β*. This is a consequence of rheological properties of a medium.1.).24. This effect is frequently used in technology where liquids are modified to impart elastic properties. exchange equipment. The following new effects are observed here: the position of the point of stream diversion becomes variable and moves upstream. polymer solutions. This range covers the transition zone from laminar to turbulent flow.
can they be considered as independent or are at least some of them a consequence of the same inherent mechanism? .2 GENERAL PRINCIPLES Formulation of rheological equation of state requires answers to the following questions: • rheological effects are observed (as a rule) in rather simple unidimensional deformations . loses its fluidity and begins to slip from a solid wall of a channel.106 Rheological equations of state • it leads to a very strong change in rheological properties of matter during its deformation • at least in some cases. That is why effects related to transitions can be classified as phase nonlinearity in rheological behavior. polymer becomes insoluble (it means that transition into a twophase system takes place) and polymer precipitates from solution. this effect is well known in stressed rubbers. moving along a channel. They are: • necking . polymer.how to describe them in threedimensional space? • many different effects coexist . Crystallization under deformation in loaded parts radically changes their mechanical properties and can lead to an unexpected breakage during operation.at high stresses. further stretching occurs through transition of an initial width into a uniform narrow “neck” • orientational dewetting (or phase separation) . Phase and relaxational transitions caused by deformations lead to very sharp changes in rheological properties of a material. This phenomenon is caused by flowtorubbery state transition • orientational crystallization . 4. similar effects were observed in shear when phase transition shifted along the temperature scale on increase in shear rate • spurt in flow .deformation can shift temperature of equilibrium crystallization and thus it influences kinetics of isothermal phase transition. There are some very typical and practically important situations observed in deformation of polymer solutions and melts related to transitions caused by deformations and therefore treated as rheological effects.at very high rates of extension of some polymer solutions.formation of a sharp contraction in uniaxial stretching of many amorphous and crystalline polymers at some critical deformation. several rheological effects discussed above can be explained based on the idea of phase or relaxational transition occurring as a consequence of deformation.
The limitations will be discussed below. It has been known for years that mechanical properties of even such old and popular material as cast iron are different in extension and compression. i. used to generalize different experimental results. whereas rheological equations of state for main groups (types) of materials will be analyzed in Chapters 5 and 6. for example. That is why. There are some general limitations for rheological equations of state to produce compatible stress versus deformation relationships for different geometrical modes of deformation. Each such set of data can be described by an empirical equation. it will be demonstrated that stress versus deformation (or rate of deformation) equations written above can be treated as consequences of some general rheological equations of state. In particular. These different equations of state give nonequivalent predictions for other deformation modes. equations for different geometrical modes of deformation must be compatible.. in order to establish the correctness of the equation of state. it is necessary to have experimental data from several different geometrical modes of deformation. This means that it is incorrect to predict behavior of this material in engineering application based on results of measurement of its properties in extension if material actually works in compression mode.A. in uniaxial extension and simple shear. Then both stress versus deformation equations must be considered as consequences of a general rheological equation of state of a material.e. illustrating the above problem in regard to properties of anisotropic materials. In other words. the same equations for onedimensional deformation can be obtained from quite different rheological equations of state. the same experimental data can be generalized in a different way. Let us discuss characteristic and important cases. not contradictive? Let us assume that sets of experimental data were obtained for different conditions of deformation. Moreover. Malkin 107 • rheological properties of a material are measured under some chosen conditions . Ya.is it possible to predict behavior of a material in other situations? What is the minimal range of experiments necessary to make a valid prediction for a full set of different stress states? • are the empirical methods. The final interpretation would be simple if both observed cases of rheological behavior of the same material would not offer two different manifestations of inherent properties of matter. .
it is necessary to carry out a set of different experiments for various geometries of deformation.50 and Coleman et al. and in such a case. Modulus of elasticity (and in fact all other physical properties) of monocrystals depend on orientation of an applied force in respect to crystallographic axes and it is quite possible to find some different values of modulus which depend on a type of crystal symmetry. it is still possible to discuss observed or predicted effects in a convenient coordinate system using tensor components as compounded variables. within the limit of small deformations. In real polycrystalline material. All this means that attempts to build the rheological equation of state of such anisotropic materials. They should describe the most general result of action of force. it is necessary to limit the use of tensor components for formulating rheological equations of state because physical laws must not depend on choice of coordinate system. This idea. modulus and all other mechanical properties depend on orientation of a force in relation to orientation of reinforcing fibers and their arrangement. General principles of constructing rheological equations of state were introduced in modern rheological literature in some fundamental works. which can be called the principle of coordinate invariance. In reinforced plastics.49 Truesdell.108 Rheological equations of state The situation becomes even more complex if one considers properties of monocrystals or reinforced plastics. are absolutely futile. this effect is averaged. Instead. but it is not for monocrystals. The first result of deformation can be accumulation . But modulus of elasticity of anisotropic materials must be treated as a tensor by itself. viscoelastic behavior or thixotropy). primarily by Oldroyd. In order to pursue this principle. If the equation is written in invariants. based on results of onedimensional experimental data. requires all rheological relationships to be formulated through invariants of an appropriate tensor but not through their components. First of all. Anisotropic properties of material can be considered. it is convenient to introduce two fundamental physical concepts related to deformations.51 The principles must be followed to assure that at least some of the equations used for describing rheological effects in deformation of real materials have physical meaning and the aboveformulated questions receive proper answers. interpretation is a part of classical linear theory of elasticity. Anisotropy of material properties is a particular kind of rheological behavior of a material and it certainly does not exclude any particular direction of all other rheological effects (for example.
because both values are physical objects not connected to any coordinate system. it can be viscosity or modulus of elasticity. if during deformation only part of the work produced by external forces is stored in a material and the other part dissipates.A. a material is a pure viscous liquid. which is a specific stored energy (energy related to the unit volume). and it can be called an elastic body. as functional invariants of kinematic and/or dynamic tensors.e. but dependencies of the constants characterizing conditions of deformation must enter into rheological equations of state only in the form of functions of tensor invariants. its irreversible transition to heat. W. physical laws should be related to the definite site (point) of a material in a form that allows one to follow material moving in space. It means that a rheological equation of state must describe behavior of a material. This stored energy is characterized by the value of elastic potential. The concepts of elastic potential and heat dissipation are very fruitful for formulating rheological equations of state. met in rheological equations of state. W ≠ 0 and A = 0. These three types of rheological behavior will be discussed in the three subsequent Chapters of the book. i. In the next step. regard . When these concepts are used in rheological equations of state. i. This effect is characterized by intensity of heat dissipation. They can change under deformation. Certainly. which is a quantity of heat produced in a unitary volume of a material. • Finally. These scalar values are physical properties of an individual material. but not of their components. A ≠ 0 and W = 0. a material has pure elastic response. Ya.. • If during deformation.. Introduction of the concept of elastic potential and intensity of heat dissipation gives grounds for a very general classification of different materials: • If during deformation. For example. they must be represented as functions of invariants to follow the principle of coordinate invariance. W ≠ 0 and A ≠ 0. The direct consequence of the principle of coordinate invariance is the necessity to express scalar values.e. if the equation of state is formulated as a dependencies of W and A on invariants of kinematic or/and dynamic tensors. Malkin 109 of work of external forces in the form of elastic energy. The second possible result of deformation is dissipation of work of external forces. This can be invariants of kinematic (deformation or rate of deformation) or dynamic (stress) tensors but not their arbitrary components. A. a material is a viscoelastic body. it is always possible to arrive at the relationship between their components.
Also. Water and paint are both liquids but with different specific behavior at various levels of stress. one of them is a liquid and the second is a solid. which is called a principle of local action. This approach has already been mentioned in Chapter 3 in our discussion of large deformations and is called the principle of material objectivity. it is considered as a general rule that only shortrange interactions are important. Although the abovecited principles are a general basis for formulating rheological equations of state (constitutive equations) of various materials and are considered as objective laws. the idea of local action can be invalid.e.. For example. it is possible to find real physical examples which do not obey some of them.. stating that material has memory of its prehistory (i. that is .e. the difference of two materials with similar rheological properties (i. expressed by the equivalent rheological equations of state) is reflected in absolute values of scalar coefficient entering the equation. Second.110 Rheological equations of state less of the possible motions of an observer. There are some other ideas which are also accepted in constructing rheological equations of state.. for liquid crystals and other materials possessing inner macrostructure. stress and deformation behavior at some point are influenced only by the nearest neighbors of this point. This is called a principle of determinism. It is therefore important to answer the following question: where is the place of individual properties of a material? There are two levels in answering this question. First.e. the manner of stress and deformation changes can influence the current state of material) but material cannot predict future events.e. There is an easily grasped idea. For example. Rheological equations of state must describe mechanical behavior of all possible real materials. which cannot be neglected. and the difference in their properties is reflected by the necessity to use quite different rheological equations of state for description of their mechanical behavior.. water and steel are different materials. The direct consequence of this principle is the requirement of transformations of deformation and stress tensor from moving to a fixed coordinate system (according to the rules of tensor transformations) in order to give an observer the possibility to see what happens with a material. i. the Newton or Hooke Laws. the difference between behavior of various media is reflected in the form of a rheological equation of state used to describe peculiarities of their deformational properties. i.
The most important and evident rheological effects are: • nonNewtonian viscosity . one encounters many “new” effects compared with “ideal” models of a linear liquid (Newtonian liquid) or a linear solid (Hookean solid).3 CONCLUDING REMARKS Investigating deformational properties of real materials. particularly the Poynting effect .. i. which is not related to the classical Reynolds inertial turbulence but connected with elasticity of a flowing liquid. These effects must be treated as special rheological phenomena.complicated stress versus deformation dependence and consequences of geometrical nonlinearity. 4. viscoelastic behavior. Understanding their origin.dependence of apparent viscosity calculated as for Newtonian liquids for a particular geometry and flow conditions for different rates of flow • plastic behavior . It can have numerous and interpenetrating manifestations: thixotropy and rheopexy. delayed deformation after stress application (creep) or remaining stress after applying deformation (relaxation) • anomalies in uniaxial extension . i. dilatancy. and quantitative description are the main problems discussed in theoretical. Malkin 111 why we need to use different rheological equations of state for these two forms of matter. particularly melt fracture. reversible volume changes under shearing.existence of normal stresses in shear flow. or appearance of a threedimensional stress state in unidimensional deformation • transient (or timedependent) behavior.e. increase of longitudinal (extensional) viscosity as a function of deformation and rate of extension • flow instability. Finally.lack of deformation if stress does not exceed some critical level • Weissenberg effect .extension of twisted wires. under applied stresses. though both of them are liquids.. i. its destruction or building.probability of uniform stretching at large extension ratio. water and oil are both Newtonian liquids and the distinction of their behavior is hidden in the difference of their coefficient of viscosity.e.A. correlation with inherent structure of matter. appearance of secondary flows. and applied rheology.e. Ya. and so on • nonlinear elasticity as a result of large elastic deformations . . experimental. reversible change of inherent structure of matter..
such as viscosity or elastic modulus. It is worth noting that in discussion of structural nonlinearity. Amorphous phase separation is observed in flowing polymer solution or rupture of viscoelastic stream (“melt fracture”) which occur at high rates of deformation. all rheological phenomena can be treated as nonlinear effects.112 Rheological equations of state Generally speaking. which can be called phase nonlinearity. This type of rheological behavior. and it is the cause of the Mullins effect. Typical results of such effects were discussed in Chapter 3. it is useful to add thermodynamic arguments to rheological considerations. for example. during polymer crystallization in extension. Structural nonlinearity can be one of the reasons for nonNewtonian viscous flow. Different rheological effects which are nonlinear phenomena originate from three general principle causes:52 • Nonlinear effects can be caused by geometrical reasons and can be nothing more than a direct consequence of large elastic deformation. represented by the Newton and Hooke Laws. . or large elastic deformation. At different stresses available at various rates of deformation. it is useful to add kinetic arguments to rheological considerations. incomparable materials are encountered. Such an approach allows one to exclude nonlinearity. It is worth mentioning that in discussion of phase nonlinearity. Nonlinear effects of such kind are observed in static (or equilibrium) conditions or in slow flows. It is reasonable to distinguish between different “degrees” of nonlinear behavior. This type of nonlinearity is the most typical for colloidal systems and filled polymeric materials. is encountered. Rheological properties of material in different phase or relaxational state are quite different because of changes along the transition. • Nonlinear effects can be related to changes (or “rupture”) of the inherent structure of material. concluding that it is necessary to introduce other measures of deformation to characterize the deformed state of material. • Strong nonlinear effect can be observed if material transits into a new relaxational or phase state due to the action of deformation. It is reasonable to think that the Weissenberg effect (at least within the limit of very low rates of deformation) and the Poynting effect are two main consequences of geometrical nonlinearity. bearing in mind that they manifest themselves as a departure of mechanical behavior of real material from the prediction of linear models. having new values of essential parameters.
but how?).. a certain level of deformation rate is sufficient for appearance of nonlinear behavior for a part of a material. For example. it consists of components of different rheological properties. i. As a general rule. For example. and the other type due to rupture of the structure of a filler. but this level of deformation rate might not be adequate to cause nonlinear behavior of other components of the same system. Malkin 113 Based on the above discussion. It means that in real practical application. although one of the most interesting characteristic rheological effects is a limited probability of maintaining onedimensional stress state for some materials. they need to be treated as related consequences of the single relationship between forces and deformations . i. filled polymer melt can manifest nonlinear behavior of one type. characterized by the following terms: geometrical weak static structural strong kinetic phase breaking thermodynamic Many real materials are multicomponent compositions. Experimental points obtained under different conditions of measurement (stress versus deformation or/and versus time) can be approximated by different equations. Ya. it is possible to build a hierarchy of nonlinear rheological effects. flow in shear and extension must correlate . It is also possible that different modes of nonlinearity are characteristic for various components of complex material.e. any real polymer is polydisperse.. Thus. abovementioned types of nonlinearity can appear at different conditions of deformation. superposition of various nonlinear effects of different types can be expected.e. Thus.A. the central problem in rheology is the compatibility of equations used for quantitative description of various rheological phenomena. due to particular properties of a viscoelastic polymeric matrix. There are two sides to the problem: • it is important to relate the explanations to analogous phenomena. Different components of material can behave differently at the same rates of deformation. but observed for different geometrical modes of deformation (for example. rheological phenomena are observed in analysis of onedimensional deformation.
that is why the rheological equation of state must be formulated. In spite of all these limitations. These limitations are expressed as the following principles: • coordinate invariance . which influences its behavior in a current moment. In construction of rheological equations of state. There are two possible general types of body reaction on the action of external forces: • storing the work in the form of elastic potential • irreversible loss of this work by heat dissipation. and this is the case of viscoelastic materials. not in the form of components of stress and deformation tensors. for example.a material can remember its past.only the nearest surrounding may influence behavior of a body at a point not the events happening far from this point. nonNewtonian flow. normal stresses in shear. In accordance with these fates of energy which was delivered by the work of external forces. the elastic potential and intensity of heat dissipation must be expressed as functions of invariants of kine . In this aspect.behavior of a medium does not depend on choice of a coordinate system.behavior of a medium does not depend on movement of an observer or a body as a whole • determinism . The intermediate situation when the work done is partly stored and partly dissipated is also possible. but does not know future events • local action . There are some important (physical) limitations. The first is necessary for industrial and technological application of rheology. it is very important to choose equations which are not too complicated to be used for practical calculations and which can be correlated with the physical structure (or content) of matter. but as their invariants • material objectivity . determining the fact that not every analytical equation can be used as a rheological equation of state. and large elastic deformations in the quest to understand their common source. freedom in constructing rheological equations of state is rather wide. and the second is of basic value if one considers rheology as one of the fields of physical chemistry offering background for objective quantitative characterization of the properties of matter. Therefore. the concepts of rheological equation of state occupy the central position in the description and generalization of experimental data. we can distinguish between elastic (solid) bodies and viscous liquids.114 Rheological equations of state • it is of importance to correlate different rheological effects.
G. Kolloid Z. Nature. 640 (1919). 517 (1976). 13. E. 36. From practical or technological point of view. Ind. C. 2B. Acta. 19. 20. Wiley. 4. J. K. A. G. i. Vinogradov. Eng. Doklady Akad. Trouton. Armstrong. 34 (1980). Phys. Assoc. Nadai in Plasticity. Eds. the difference between them is quantitative rather than qualitative. and R. Ostwald. Malkin 115 matic and/or dynamic tensors. Physique. W. Ph.M. A. Rheol. 3. The last general remark is rather evident for a rheologist but may look strange for a nonprofessional or even for an engineer. Soc.. C. Bingham and H. 7. 154. K. Pergamon Press. Rheol. M. R. McGraw Hill.. 1968. J. 15. A. 2. J. D. J. C. Waele. 1959. Hill in Plasticity. Macmillan. 10. Casson in Rheology of Disperse Systems. 17. Thesis. Yasuda. 213 (1992). Cross in Polymer Systems. P. one can definitely distinguish between solid bodies and fluids.A. 9. 326 (1906). 12. 31. 230 (1971). Meissner. A. Prager and P. Ed.. Claderon Press. 33 (1923). G. 415 (1978). F. 8. Carreau. Acta. W. R. Commun. University of Wisconsin. 671 (1964). customizing properties of a material. Malkin. Proc. Kargin. 15. 99 (1925). Mill. 248 (1925). and V. they are qualitatively different entities. G.. 599 (1989). Royal Soc. Ser. 11. W.. and the values of scalar coefficients (“material constants”) which are parameters of this equation. Bingham. New York. Larson. V. J. E. 159. Polym. V. 9. Wetton and Whorlow. Laun and H. 1421 (1964). New York. 1951. M. Ya. Assoc. J. Proc. 310 (1947). Deformation and Flow. Ya. 5. E. Colour Chem. .. 7. Green.. Meissner. 1950. Hodge in Theory of Perfectly Plastic Solids. Testing Mater. Oxford. 77. P. II. Malkin. Oxford. C.4 REFERENCES 1. Amer. E. C. Weissenberg. Rheol. in the great majority of cases. 14. Proc. and it is preferable to qualify them. 1931. H. 19. Acta. 1969. For rheology. Linster and J. Makromol. ibid. 190. The difference in mechanical behavior of various materials is reflected in the form of the rheological equation used. Chem. Rheol. Acta.e. A. 36. Rheol. Ya. 6. Ya. Sci. J.. 47 (1905). 10. 33. Vinogradov and A. A. Ostwald. Münstedt. R. 4. Nauk USSR. 6. Y. The difference appears as a consequence of the ratio of the time scale (duration) of observation and the inherent (characteristic) time scale of a material. N. Ind. De. 1263 (1981). 335 (1968). Cohen. Oil. Kolloid Z.. Acta. Chem. not into solids and liquids but as materials with dominating solidlike and liquidlike behavior under real conditions. Plotnikova. 159 (1985). Malkin.
Ver Strate and W. Polym. 429 (1886). Ya. 309 (1944). Schowalter... Shinner. S. A. Nature. Mark. Res. Hermann and Co. ibid. Thomson) in Elasticity. 469 (1885). 45. W. 28. 271 (1975). 22. Macromol Chem. Soed. 38. Ogden. Lord Kelvin (W. L. Mullins. 44. Taylor. 554 (1957). II. 7. Eng. Tschoegl. Vinogradov.. Lord Rayleigh. 689 (1969). S. Mark. 20. Compt. A. 30. Poynting. Kuhn. and N. Tobolsky. E. Fluid Mech. Minsk. 21. H. N. A. 15. Appl. Benjamin. M. 1949. Sci. Khimia.. Sci. 251 (1951).. Phys. W. J. Phys. Trans. 289 (1923). I. 1967. Soc. Congr. Toms. Bartenev and T. Eirich. Barus. H. J. 961 1041 (1840). 45. . A. B. Acta. Collins in Rheology. R. Rivlin and D. 18. Polym. 4. Appl. Goldin. J. Rheol. Shrada. J. 19.. Soc. 23. 16. Colloid Sci. Sternstein. Symp. J. J. 225 (1971). Ya. Proc. J. 42. J. 34.. 30.. 10. AIChE J. J. Christensen. Ed. Mag. Am. Royal Soc. 1970. First Intern. 582 (1940). Blasius. Ed. Pfeffer. A. V. G. 10. 26.. Paris. Petrie and M. 65. White. H. J. Chem. and R. F. 93 (1934). AIChE J.. vol.. North Holland Publ. Proc. 2. 12. Soc. 87 (1893). H. Freundlich in Thixotropy.116 Rheological equations of state 16. London Math. New York. 20 (1960). F.. 1061 (1972). O. Theory and Applications. A. I. 546 (1909). Guth. S. J. 1935. Academic Press. 8. G. Ser.. Blatz. Philippoff. 175 (1968). W. 33. V. M. 326. Kazanovitch. H. 223. Hüttig and Wept. Fluid Mech. Sci. 27. 22. M. R.. Denn. deutscher Ing. 41. 19.. Roy. vol. R. M. E. J. 32. Rheol. S. G. Moscow. P. 29.. J. p. 1167 (1842). J. Ed. 30. 82. Roy. S. ibid. Fluid Mech. V. Malkin and S. 46. G. 253 (1946). Eirich. A243.. 68. A.. 24. Phys. 40. Bauer and E. G. Mikowycz.. 15. Trans.. Giesekus in Progress in Heat and Mass Transfer. 39.. New York. C. E. W. L. Chem. W. 20. 45. Polym. Adv. 1875. H. L. Roy. 413 91973). 595 (1958). Monatsch. Plast.. 135. J. Rubb. Poisseuille. Kulichikhin in Rheokinetics. Trans. M. V. . 4 (1879). Soc. Virk. G. Rheol. 17. Tordella in Rheology. Leonov in Advances in Polymer Rheology. M. L. 12. 11. 209 (1976). 751 (1962)... 9th Ed. 115 (1973).. Encyclopedia Britannica. J. 275 (1947). 35. 534 (1912). 37. Ser. 112 (1841). Mooney. 357 (1973). J. Guth and H. Kolloid Z.. Reynolds. 11. 21. 36. Polym. A. Yerushalmi. 423. J. Soc. p. Theory and Applications. 2 (1934). Letters. Z. 625 (1975). R. 2. Silverman. Polym. P.. ibid 9. and W. Appl. rend. Soc. Phys. R. 5. Lazurkin. 12. 639 (1912). Malkin and A. J. S. A2. Rheol. R. P.. 195 (1972). Phil. 38. 1969. 18. 25. H. 565 (1972). Academic Press. de Ver. 86. Ya. Proc. vol. Malkin. C. 31. J. Saunders. Luikov. 145 (1974). Soc. James. 1994. T. 18. J. J.. Vysokomol. Ongchin. S. and H. Heidelberg. Amsterdam. 267 (1974). 43. B. Pure Appl. 2. Soc.. Vinogradov and A. 5... Trans. and A. R.
Truesdell in Principles of Continuum Mechanics. A.. 671 (1892). 1961. Phys. 47.. 1966. Ya. Roy. 35. B. Malkin. Congr. (1890). 200. J. Ann. 185 (1868). 34 (1995) in press. G. ibid. C.. 117 W. Wiss. Phys. A. Abh. Markovitz. Seville. 4th Eur. Soc. D. Voigt. Mag. H. Rheol. Ya. and W. 36. Ser. . 52. 49. 50. 129. Maxwell. Rheol. 1994. Springer. Proc.. J. 523 (1950). 202. Göttingen. Oldroyd. Texas. Ges. 345 (1950. 51.. Coleman. Noll in The Viscometric Flows of NonNewtonian Fluids. 48. Acta. SaconyMobil Oil Co. Berlin.A. Malkin 47. C.
For example.A. Nobody doubts that water or gasoline are liquids. It is necessary to introduce a more rigorous definition and compare behavior of real materials with such a definition.. e. which is called yield stress or yield point.1 DEFINITIONS The concept of a liquid seems rather evident. it covers two types of behavior: viscous and viscoplastic. unrecoverable deformations appear only when stress overcomes some definite level. Malkin 119 5 RHEOLOGICAL VISCOUS FLUIDS 5. i.g. Nevertheless.e. But what about tooth paste or adhesive? These simple examples show that it is not sufficient to imply that a liquid is a material which can flow. we undoubtedly create unrecoverable deformations.. In the first case. In the second case. We may think that a liquid is a material which undergoes unrecoverable (irreversible) deformations. unrecoverable deformations (or flow) can be detected at any stress. punching of golden articles. Indeed. regardless how small it may be. It should be noted that the definition must encompass all real materials. These examples show that the above definition is too wide. one would need to consider metals as liquids because during some technological operations. at stress exceeding yield stress as a flow. wiredrawing of silver or rolling steel ingots. . changes in shape remain after the action of external forces is removed. It means that a viscoplastic medium can be called a “liquid” only with some precautions. Ya. treating deformation of viscoplastic materials. looks quite reasonable.
and time of observation. at very low stress. Nevertheless. liquid viscoplastic media (“liquids”) can store residual stresses equal to the yield stress.e. even though they exist. The possibility to flow under infinitesimal stress means that a liquid at rest cannot store any stress. This assumption may have rather serious consequences. For example. no stress should exist in the whole volume of the body. flow inside a body having motionless boundaries can appear as a result of temperature gradient in a liquid. etc. bearing in mind that in the scale of eternity. Indeed. this idea can also be considered as a definition of a liquid state. That is true. tobs. Contrary to such behavior. tinh. This characteristic inherent time. Second: Perhaps during the period of observation (or experiment) unrecoverable deformations are so small that they cannot be detected. three. Formally. the Lord really can observe flow of rocks (mountains). De: De = tobs/tinh . This is true with some reservations only.. and the general answer to the problem raised by the theoretician lies in the comparison of “inherent” time scale of a material. does not occur. can be treated as time of relaxation. If an experiment is prolonged. one deals with a viscoplastic liquid. we can introduce the dimensionless criterion tobs/tinh (see also Eq 4. this definition looks quite acceptable. tinh. i. but the yield stress is so small that it cannot be observed under experimental conditions but can be attained if conditions change.. Rheologists like to cite a famous exclamation by the Bible’s Deborah: “The mountains melted from before the Lord”. it is never certain that the level of stress attained in an experiment is sufficiently low to assume that a material is a liquid from an experimental point of view. But an experimentator may ask two questions: First: Perhaps if stress is decreased by one (two. called the Deborah Number. Indeed. if outer boundaries of body (treated as a liquid) are motionless. Then.) orders of magnitude.17).e. i. time necessary for recovery of a stable structure state after removal of external forces. it is possible to reach the yield point at which flow. flow of a material under investigation should occur. in the case of any liquid.120 Rheological viscous fluids We can also define a liquid as a material which can flow (or is capable of unrecoverable deformations) under the action of infinitesimal (small) stress. Doubt was expressed even for such a classical liquid as water.
In essence. Any action is connected with energy consumption. because viscous resistance to movement means heat dissipation of the work produced by the forces applied. A viscous liquid then. Certainly. Malkin 121 If De > 1. which is characteristic for viscous liquids. Two types of energy used for material deformation might be considered: the energy stored in the material and its return after the removal of external forces.A. can be defined as a medium deformed in such a manner that energy needed for deforming completely dissipates in the process of deformation. without any elastic effects. In the opposite time scale (when De < 1). but as a kind of behavior. a very general definition of a liquid might be constructed on the basis of energy concept (see Section 4. Finally. of a viscoelastic liquid. one should consider liquidlike behavior of a material. it means that no energy source for further deformation exists in the material after the action of external forces ceases and that is why deformation cannot be recovered (no driving force exists for the process). We shall not consider such liquids here. The energy concept dividing materials according to their reaction to the work of deformation is the most general approach of characterization of a material type. only a viscous liquids. We then can define liquid as a material which relaxes very quickly. which answers the second question regarding rigorous definition of a liquid. in particular. intermediate cases may exist when energy of deformation is partly stored in a material and only part of this energy can be dissipated. In this sense. not as a state of a matter. material behaves like a liquid. Ya. which occurs when tinh is small and relaxation happens very quickly (in comparison with time of observation). since all of Chapter 7 is specifically devoted to media properties having a combination of viscosity and elasticity. The second reaction consists of energy dissipation by its conversion to heat. Therefore. Such a concept is not related to any considerations of local values of stresses and deformations and does not need to be related to observation of material behavior in coordinate axis. unrecoverable deformations cannot be detected and we cannot discover flow and treat a material as a liquid.2). Such is the case of a viscoelastic body. and this definition gives the concept of liquid. the energy approach is invariant to a coordinate transformations and satisfies general requirements of rheological equations of state. Storage of energy is characteristic for an elastic medium (elastic behavior in rheological media is discussed in Chapter 6). .
We shall now discuss a general approach to the concept of Newtonian liquid. A. bearing in mind the common principles of rheology formulated in Chapter 4. one needs to express the intensity of dissipation.2] [5. as a function of deformation rate in a rheological definition of a liquid. Intensity of dissipation. It is very easy to convert this equation.122 Rheological viscous fluids 5. A. Eq 1.2 NEWTONIAN LIQUID The idea of Newtonian and nonNewtonian behavior of liquids was introduced in discussion of rheological effects describing the development of rheology as a separate branch of natural science (Chapter 4). This general approach allows for the following definition of the Newtonian liquid: A = − 4 ηD 2 where D2 is the second invariant of the rate of deformation tensor. The A is a physical object invariant to the choice of a coordinate system. γ ij are components of the rate of deformation tensor.1. Onedimensional (trivial) definition of Newtonian (or NewtonStokes) liquid is given in Eq 1.3] .1] which refers to the standard definition. Further discussion concerns the concept of a Newtonian liquid in an invariant form. In order to apply the definition of a liquid as a material for which all work done in deformation dissipates. [5. using tensor notation: σ ij = 2ηD ij and for simple shear & γ = 2D ij = ∂u 1 ∂x 2 [5.1 for simple shear. and η is (Newtonian) viscosity. which is why the rate of deformation also must be represented through its invariants. is expressed as & A = ∑ σ ij γ ij & where σ ij are components of the stress tensor.
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The second invariant of the rate of deformation tensor is & & & & & & &2 &2 & 23 D 2 = γ 11 γ 22 + γ 11 γ 33 + γ 22 γ 33 − ( γ 12 + γ 13 + γ 2 ) Combining the expressions for A and D2 with the definition, Eq 5.3, and considering coefficients in tensor notations, one comes to the starting formula of the NewtonStokes liquid, Eq 1.1. It is interesting and instructive to draw the relationship between stress and rate of deformation for uniaxial elongation based on the general (invariant) definition, Eq 5.3. Stress tensor for uniaxial extension is expressed as σ 11 = σ E where σ E is the drawing stress and all other components of the stress tensor are absent (equal to zero). The rate of deformation tensor has only diagonal nonvanishing terms. It should be assumed that a liquid is incompressible. In this case (see Chapter 2), the first invariant of the deformation tensor equals zero. Thus, its time derivative (i.e., the first invariant of the rate of deformation tensor) also equals zero and we have & & & D 1 = γ 11 + γ 22 + γ 33 = 0 For an axially symmetrical body, for example, for a cylinder, 1 & & & γ 22 = γ 33 = − γ 11 2 Therefore, A is evidently equal to & A = σ 11 γ 11 For uniaxial extension, considering relationship between components of the rate of deformation tensor, we have [5.4]
124
Rheological viscous fluids
D2 = −
3 & γ 11 4
which leads to the following relationship between drawing stress and rate of deformation in uniaxial extension & σ E = 3ηγ 11 [5.5]
The coefficient between normal stress, σ E , and the rate of deformation is called elongational viscosity, λ, and according to Eq 5.5 λ = 3η which is Trouton equation, discussed above. In fact, it demonstrates that both equations (Newton and Trouton equations) represent the same type of rheological behavior, i.e., the Newtonian liquid (liquid obeying the Newton Law in shear) will obey the Trouton Law in uniaxial extension and vice versa. The same result can be obtained, not only by using the idea of intensity of dissipation, but also by exploring the decomposition of stress and the rate of deformation tensors into spherical and deviatoric parts. The stress tensor can be decomposed into spherical and deviatoric parts in the following manner: σ E 0 σ= 0 0 0 2 0 0 = σ E δ + σ E 1 0 0 0 0 ij 3 3 0 0 0 0 1
where the first member is a spherical part (negative hydrostatic pressure) and the second term is a deviator of the stress tensor. For uniaxial stretching of a symmetric body, using the above mentioned relationship between components of the rate of deformation tensor, we can write:
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125
& γ 11 0 & γ= 0
0 & γ 22 0
0 2 0 0 = 1 γ 1 0 & 11 0 0 2 & γ 33 0 0 1
The spherical component in the rate of deformation tensor is absent which is the consequence of the incompressibility of liquid. The spherical part in the stress tensor is present but its value is immaterial for rheological behavior of liquid (regardless of the hydrostatic pressure, the volume of liquid remains unchanged). If we compare deviatoric parts of both tensors, we again come to the Trouton equation for elongational viscosity, which equals 3η. The general definition (Eq 5.3) of the Newtonian liquid also allows one to calculate elongational “viscosity”, now measured in biaxial extension. Let us find the relationship between drawing (normal) stresses, σ E = σ 11 = σ 22 , & & & (σ 33 equals zero) and rate of deformation, ε = ε 11 = ε 22 . According to Eq 5.4, in & this case, ε 33 = 0. For biaxial extension & & A = 2σ E ε ; D 2 = − 3ε 2 and then in accordance with fundamental Eq 5.3, we have & σ E = 6ηε [5.6]
It is possible to treat the coefficient of this Equation (i.e., the coefficient of proportionality between stress and rate of deformation) as elongational viscosity, in the same manner as done for the Newton and Trouton Laws. Then, the biaxial “elongational viscosity” equals 6η(not 3ηas in uniaxial extension). These two examples (uniaxial and biaxial extension) show that “viscosity” of a liquid can be different, depending on its definition. These simple examples demonstrate that results of different experiments can be considered as consequences of the same rheological equation of state (constitutive equation) if formulated in a generalized (tensor) form. Also, it is clear that invariants must be used in the formulation of rheological equations of state for liquids in relationships between components of stress and rate of deformation tensors.
126
Rheological viscous fluids
A Newtonian liquid is the simplest incompressible linear liquid and its rheological properties are completely described by a single parameter, its shear viscosity. In fact, it implies that a liquid is isotropic. But anisotropic liquids, i.e., liquids with properties dissimilar in different directions, can also exist (for example, in liquid crystals). Even if such liquid is linear, a single coefficient of viscosity is not sufficient for complete representation of its viscous properties. If we measure viscosity by creating shear at different planes, we will obtain dissimilar values of “viscosity”.1 For such anisotropic liquids, it appears necessary to characterize their properties by a tensor of viscosities,1 though practical determination of components of this tensor can appear a very complex problem. In order to give an impression of the possible range of changes of viscosity for real liquids let us list some typical values: Gases Water (at 20oC) Sulphuric acid Lubricating oils Glycerin Oligomers Glues, paints Melts of thermoplasts Rubbers and rubber compounds Bitumens Melted inorganic glasses Glassy liquids 0.1 mPa⋅s 1 mPa⋅s 30 mPa⋅s 0.1  3 Pa⋅s 2 Pa⋅s 10 mPas  10 Pa⋅s 1  200 Pa⋅s 100 Pas  100 kPa⋅s 10 kPas  10 MPa⋅s 100 kPas  100 MPa⋅s 1 MPas  100 GPa⋅s 100 GPa⋅s
The viscosity of liquids can vary in a wide range of values exceeding 15 decimal orders.
5.3 NONNEWTONIAN LIQUIDS
According to the discussion in Chapter 4, any viscous liquid is a medium for which intensity of heat dissipation in deformation is expressed as a function of kinematic and/or dynamic invariants. The simplest equation representing the idea is the Newton Law written as Eq 5.3. Certainly this equation does not describe other effects characteristic for nonNewtonian liquids.
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The formal way of generalization was proposed by Rivlin2,3 who advanced the idea that intensity of energy dissipation is a linear function of the second and third invariant of the deformation rate tensor. This assumption can be written as A = − 4 ηD 2 + η c D 3 [5.7]
where the first member is Newtonian input to stress tensor and the second one is a nonNewtonian addition. The coefficient of proportionality, ηc , is called “crossviscosity”. The dissipative function (Eq 5.5), describing behavior of the Reiner liquid, predicts the existence of normal stresses (Weissenberg effect) as a secondorder phenomenon (normal stresses are proportional to the squared shear rate) but no other special rheological effects, including nonNewtonian viscosity. Moreover, the predicted sign of a normal stress is opposite to experimentally observed values. It is important to emphasize that in the Reiner liquid, normal stress appears for pure viscous medium (stored elastic energy is absent) but is not related to rubbery elasticity of a material. It also contradicts the experimental evidence, because we know that normal stresses always accompany, or are accompanied by large elastic deformations. The model of the linear Reiner liquid does not reflect the mechanical behavior of any real material known to date; nevertheless, this model is very interesting for two reasons: firstly, it shows the rigorous way of generalizing a rheological equation of state through introducing different invariants of the kinematic tensor; secondly, it shows that not every formal way of constructing rheological equations of state leads to realistic results. Bearing this conclusion in mind, the Reiner viscous liquid model mostly has historical relevance. Development of ideas concerning construction of rheological models of nonNewtonian behavior takes various routes. First of all, the third invariant was not used as an argument in rheological equations of state. Then the second invariant of the rate of deformation tensor was used as an argument for a scalar material constant, identifying properties of a material. It reflects the idea that deformation influences the inherent properties of a medium, and this is the reason for nonNewtonian behavior.
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Rheological viscous fluids
For onedimensional deformation, this concept can be written in the following form & σ ij = 2η(D 2 )γ ij [5.8]
According to this equation, we assume that rate of deformation (expressed through its second invariant) influences apparent viscosity of a liquid. The form of the function η(D2) can vary, depending on individual properties of material. Certainly, this equation can be treated as a generalization of Eq 5.3, and in this case, it is written as A = − 4 η(D 2 )D 2 [5.9]
One of the most popular (widely used for various applied calculations) models of nonNewtonian flow is a power law, written as & σ = Kγ n Apparent viscosity in this model is a decreasing function of shear rate or shear stress η= σ 1 & = Kγ n1 = K σ & γ n
n1 n
[5.10]
and as a rule n < 1. A generalized (threedimensional) form of the power law takes the following form 1 n1 & σ ij = 2K D 2n γ ij 2 For onedimensional shear flow this equation can be written as & & σ = Kγ n1 γ where apparent viscosity is expressed as in Eq 7.10. Eq 5.10 can be applied to unidimensional axial extension of a liquid cylindrical [5.11]
The D2 can be found from equation 3& D 2 = − λ2 4 Let us suppose that. apparent viscosity is a decreasing function of shear rate (and of D2). as the invariant characteristic of a material. in fact. components of the rate of deformation tensor are 1& & & & & & γ 11 = λ . which becomes true for any viscous liquid at appropriate condition of comparison between shear and extension. one can see that if we take the condition between shear and extensional rate of deformation as 1 & & λ= γ 3 we arrive at the Trouton Law. in its elasticity. This leads to the conclusion that the increase of rate of extensional deformation must cause the decrease in apparent viscosity. Ya.A. Indeed. viscous properties of two liquids can be the same in shear but quite different in uniaxial extension. we know that for many “rheological” liquids the Trouton Law is not correct. γ 22 = γ 33 = − λ . must be decreasing as well. In this case. which is apparently not related to nonNewtonian behavior of a purely viscous liquid but is hidden in its other rheological properties. . The divergence from the Trouton Law in properties of some liquids demonstrates that the possibility of describing properties of a liquid by equation in one geometrical mode of deformation does not automatically lead to correctness of its threedimensional generalization and its application to another mode of deformation. one may expect that the function η(D2). It means that in a threedimensional generalization of the power law. γ ij = 0 for i ≠ j 2 where the first component of the rate of deformation tensor is the rate of extension. Moreover. as usual. Malkin 129 stream. measured in uniaxial extension. On the other hand.
and the yield stress. Certainly. The common question is: how to write the condition of rupture in a complicated (threedimensional) scheme of loading. if the principle stresses in a multidimensional stress field are σ 1 . Moreover. the same material being stretched in one direction begins to flow at normal stress. The criterion of yielding for different main stresses must be found. Different conditions (criteria) of the threshold of yielding (strength.SaintVenant criterion of yielding is given by . should be a function of the second invariant of the stress tensor. the influence of the hydrostatic pressure (or the first invariant of the stress tensor) is immaterial in a rheological problem. and this criterion must be formulated through invariants of the stress tensor. This approach is equivalent to the one used in the theories of strength of solids. As a general rule. It assumes that if the yield stress in simple shear is σ yE . σ yE = 0.4 VISCOPLASTIC LIQUIDS Rheological equation of state for a viscoplastic liquid was introduced in Chapter 4. Onedimensional rheological properties of a Bingham viscoplastic medium are expressed by Eq 4. the main analytical approximations used in these theories also are used for the yield stress. if pressure is not very high.130 Rheological viscous fluids 5. and σ 3 . This fact has been already mentioned in discussion of the Weissenberg effect in Chapter 4.σ E .7. the Treska . This problem is typical in finding the threedimensional criterion of strength in mechanics of rupture of solids or plasticity for solid plastic materials. if the strength of material was measured in unidimensional extension.12] Then. σ yE . The most popular and simple equation for the yield stress is based on the old idea which determines the meaning of the critical value of the maximal shear stress (the Treska SaintVenant criterion). calculated as (see relationships between normal and shear stresses in Chapter 2): σ E = 2σ yE . σ 2 . the answer to both analogous questions (regarding the strength and the yield stress) lies in the use of invariants of the stress tensor. The main problem in generalization of the Bingham equation is the formulation of a threedimensional criterion of yielding. plasticity) in multidimensional loading were proposed and used.5σ E [5.
1 ≤ σ yE . because it is possible to show that the left side of Eq 5. 2 ≤ σ yE 2 2 2 An alternative approach used for determination of the threshold of yielding is known as the von Mises criterion and is assumed as a condition of reaching some critical value of the intensity of shear stresses.13 represents (for the Hookean solid) specific energy of elastic deformation required to change the form of a body (calculated for a point).SaintVenant and von Mises criteria are rather close to each other.5.13] where σ E is the yield stress in uniaxial extension.A.14] Comparing Eqs 5.577σ E [5. one can see that Treska . Ya. It means that the material begins to flow when it has stored a critical amount of elastic energy while changing its form (not volume. It is formulated through principle stresses as 2 (σ 1 − σ 2 ) 2 + (σ 1 − σ 3 ) 2 + (σ 2 − σ 3 ) = 2σ yE [5. The term “hydrodynamic” should not lead to confusion. It is interesting to note that the von Mises criterion of yielding can be called an energetic criterion. since we do not take into account the first invariant of the stress tensor). Use of this term does not imply that it is related specifically to water (“hydro”) but to any viscous fluid. Malkin 131 σ − σ 3 σ − σ 3 σ 1 − σ 2 ≤ σ yE .1 INTRODUCTION Some basic problems of hydrodynamics are discussed below in order to demonstrate typical examples of application of rheological equations of state for main types of “rheological” liquids. The correspondence between the shear yield stress and the critical normal stress. can be written as σ yE = σE 3 ≈ 0. 5. .14.12 and 5.5 SOME BASIC PROBLEMS 5. according to the von Mises criterion.
we shall demonstrate the importance of this factor for hydrodynamic problemsolving in a volume. in the isothermal case. contrary to their solutions obtained by computational methods. with desirable accuracy. It requires one to combine the following elements: • rheological equation of state (see Chapter 4) • equilibrium (balance) equations (see Chapter 2). The use of boundary conditions is very typical and common for solving any differential equation. by computer calculations. Below. The last element is yet to be defined. which are approximate solutions. turbulence can be considered as nonNewtonian (“rheological”) flow of some special kind. even though their divergence from an exact solution can be as small as required. All examples discussed in this Section are related to laminar flow and are not applicable to turbulent flow. at the same time. we shall discuss basic hydrodynamic patterns which are most frequently observed in applications. because in a turbulent regime the NewtonStokes relationship between shear stress and shear rate is not valid.132 Rheological viscous fluids The transition from rheological equation of state (or constitutive equation) of a liquid to a hydrodynamic problem is equivalent to the transition from discussing the situation “at a point” to considering flow of a liquid in a volume. In this respect the majority of solutions discussed below are exact solutions. The solution of different hydrodynamic problems includes understanding of: • distribution of hydrostatic pressure and components of the velocity vector in space in which flow takes place. because equations of flow for practically any geometrical pattern (even very complex) can be solved numerically. for example. it is an equation of force balance only • boundary conditions. In the subsequent sections. they can be expressed by relatively simple models. This is also true for different rheological equations of state which are used for investigation of various hydrodynamic situations. The choice of examples discussed below is determined by the possibility to integrate differential equations of flow to obtain a solution in analytical form. the relationship between flow rate and pressure in flow through a channel appears to be different than predicted for a Newtonian liquid. It is done only for illustrative purposes. Meanwhile. and as a consequence. four variables are functions of four basic hy . Real situations can be very complex.
1 explains the example. 5. and pressure which must be applied to create predetermined flow rate.1. Among them are: • problems of transportation of different liquids (socalled inner problems flow of liquids inside channels with solid external boundaries) • movement of solid bodies in liquids (socalled outer problems . which allows one to neglect all changes which can happen along the xcoordinate. for rather simple geometrical forms of solid boundaries. two items on the list can be formulated for any space situation and arbitrary geometry of solid boundaries of a channel or moving solid body. output (or flow rate) of a liquid flowing through a channel. as a general rule. The problems of the third group are considered. Flow in different geometrical forms is used for numerous applications.5. It means in particular that .a liquid flow around solid boundaries) • purely rheological problems. Malkin 133 drodynamic equations (three balance equations and an equation of conservation of mass) • integral characteristics of stream. Scheme of plane unidimensional flow and system of coordinates used for formulating basic hydrodynamic equations.2 PLANE UNIDIMENSIONAL FLOW Figure 5. because they are determined by the practical value of the situation under discussion. because only for such simple forms is it possible to build an apparatus for comparison of theoretical prediction and experimental observation resulting in an evident and easytograsp result. Figure 5. Let us consider flow along the zaxis. Ya. First. such as complete force applied to a moving body. then assume that the size of parallel planes in xdirection is unlimited (at least much larger than the distance between planes equal to H).A. such as comparison of theoretical predictions with experimental observations (cannot be solved “at a point” but only for volumetric flow) or determination of constants in rheological equations of state.
V = V(y). Pressure can be a function of the zcoordinate only. below we shall use the symbol V without subscript index). Besides ∂V ∂p = 0.15. p = p(z) Steady flow is considered.. considering the boundary conditions. Vz. different from zero (therefore. =0 ∂x ∂x ∂V ∂p = 0. =0 ∂z ∂y This shows that there is only one component of velocity. there is a need for only one balance equation: dp dσ =− dz dy where σ ≡ σ yz = σ zy The lefthand side of this equation is a function of z only. Consequently.e. can be written as σ = σw − dp y dz [5. and therefore any inertial effect does not need to be taken into account and inertial members in the equilibrium equations can be omitted. Then. and the righthand side member is a function of y only.15] . It means that equality can exist if both members are constant. V can be a function of the ycoordinate only.16] [5. i.134 Rheological viscous fluids V x = 0. the general solution of Eq 5.
16) is not related to any rheological model. This type of flow is possible when one plane is moved relative to the other and “drags” a liquid. Malkin 135 where σ w is the shear stress acting (or applied) at the solid boundary (at the plane).. and L is the length of this channel. (i) Drag flow. regardless of rheological properties of a liquid.A. The last general postulate should include the gradient of pressure. shear stress is uniform throughout the whole volume between planes. It is true because as long as stress. the shear rate must be also constant (in steady flow). it is valid for any material. Assuming that dp = const dz one can write dp ∆P = dz L where ∆P is the pressure drop (difference of pressures at the ends) in a channel where flow takes place.e. then σw = F S It is important to emphasize that the general solution (Eq 5. it does not involve any rheological equation of state. Ya. but not velocity distribution. since. Because shear stress is constant throughout a gap between planes. when σ = σ w = const In this case. The important case of Eq 5. shear rate is an unambiguous function of shear stress . i. for any nonNewtonian liquid. If the area of planes is S and total tangential force F. is discussed.16 includes flow in the absence of a pressure gradient: dp/dz = 0. This type of behavior is called drag flow.
Velocity profiles in flow between two parallel planes without pressure gradient. Constant shear stress leads to a constant rate of shear. Q. in drag flow is calculated as Q= Vw BH 2 [5. The possibility to realize flow with constant shear stress is an unique method of constructing flow curves.2. The presence of linear velocity profile and constant shear rate in the gap is evident. the shear rate is determined by the ratio . The volumetric output.2. The last equation can be rewritten in dimensionless form V =β Vz where β is a dimensionless coordinate β= y H [5. where B is the size of planes in the xdirection.18] Figure 5. Varying shear stress (changing total force).136 Rheological viscous fluids dV = const dt which gives a linear velocity profile through a gap between planes: V = Vw y H where Vw is the velocity of a moving plane (velocity of the other plane is assumed to be equal zero).17) is represented in Figure 5.17] The solution (Eq 5.
and calculate shear stress as the ratio of F/S. the radius of the inner cylinder Ri. R is the radius of an outer or inner cylinder which are almost the same if the condition 5. Malkin 137 & γ= Vw H [5.1 and thus the problem is called the Couette problem. one can neglect their curvature and treat them as parallel plates. Let the radius of the outer cylinder be Ro. S = 2π Ro + Ri L 2 where L is the height of the cylinders. The experiment can be reversed: we can set velocity. Also.19] Then.21] . The system of two coaxial cylinders is then treated as parallel planes H = R o − R i . other drag flows (not only circular) are often called the Couette problem. and the condition Ro − Ri << 1 Ro [5. they can be curved into cylinders. Ya. Circular drag flow between two coaxial cylinders was investigated by Couette.20 is valid. In practical realization. The shear rate in the gap is & γ= ωR Ro − Ri [5. the pairs of values “shear stress .20] is fulfilled. F. it is not necessary to have flat planes. If the gap between two coaxial cylinders is much smaller than their radii.A. Linear velocity is expressed as V = ωR where ωis angular velocity (measured in rad/s). Vw. measure total force.shear rate” are obtained. of a moving plane.
20 is fulfilled. this configuration can be treated as an absolute method of determining a flow curve of a nonNewtonian liquid with unknown rheological properties.. σ i Ro ≡α = σ o Ri If Ro/Ri is close to 1. then we have an “almost” homogeneous stress field. the general solution for a liquid with arbitrary rheological properties does not exist. If the gap between cylinders is not small in relation to the radius of the inner cylinder. Changes in Eq 5. The most important point here is the possibility to find shear stress and shear rate independently and regardless of any rheological model. i. this method works when the condition 5.21).22) and shear rate from angular velocity (Eq 5.23] 2 where it is assumed that an outer cylinder is rotating and M is the torque measured also for an outer cylinder.22] where H is the height of cylinders (more exact: height of a gap filled with flowing liquid). velocity distribution in circular flow between two coaxial cylinders with an arbitrary (not an obligatory small) gap between them depends on rheological properties of a liquid. Certainly. Indeed. The simplest case is surely a Newtonian liq . Since M = const. expressed as M = 2πR 2 Hσ o = 2πR 2 Hσ i o i [5. The exact solutions can be found for some shear rate versus shear stress laws.e. If we know shear stress from the torque (Eq 5. This configuration is often used in viscometric practice in socalled rotational viscometers. The last equation allows one to estimate the inhomogeneity of stress field in the gap between two coaxial cylinders. or if we measure the torque applied to an inner cylinder.138 Rheological viscous fluids The existence of shear stresses leads to torque. we can easily find apparent viscosity in accordance with the NewtonStokes definition of “viscosity”: η≡ σ M(R o − R I ) = & γ 2πR3 Hω o [5.23 must be introduced if an inner cylinder is rotating. M.
one of the velocities equals zero). i.e. Special cases. Eq 5.26 is the basic equation for determination of viscosity of Newtonian liquids. viscosity can be calculated as a measure of the ratio of these parameters: η= KM ωo − ωi [5. M..cylinder rotational viscometer . are measured (in practice. In a cylinder . velocity distribution is expressed by a formula V(r) = (ωo R 2 − ωi R 2 )r 2 + (ωo − ωi )R 2 R 2 o o i i (R 2 − ri2 )r o [5.24. ωo . r. when ωo = 0 or ωi = 0.26. are formally included in Eq 5.26] The torque is the same for any value of radius. which is why the current radius.27] where K is a geometrical factor. If two parameters. does not enter Eq 5.25] where η is viscosity of a Newtonian liquid. The torque in flow of a Newtonian liquid is expressed as M= 4πηL(ωo − ωi )R 2 R 2 o i R2 − R2 o i [5. the value determined by geometrical sizes of an instrument used for measurement. In this case. Malkin 139 uid. torque. and angular velocity of an inner cylinder is ωi .A. ωo − ωi . as a general rule.24] where V is the V ϕ (circular) component of the velocity vector and r is a current radius ( Ro > r > Ri). Ya. The distribution of shear stress is σ= 2 2η(ωo − ωi )R o R 2 i (R 2 − R 2 )r 2 o i [5. and difference of angular velocities. when an outer cylinder is rotating with angular velocity.
sufficiently far from a rotating cylinder. rate of rotation. It proves the basic assumptions used in building the theory.27 is used in order to find the Kvalue for the instrument. and r a current radius (distance from the axis of a rotating cylinder).28 shows that velocity decreases to zero “at infinity”. rotation of a screw propeller in a sea). The torque applied to rotate a cylinder in an infinite volume is calculated according to the equation M = 4πηωHR 2 Rotation of a cylinder in an unlimited volume is a model case used in many real situations when a size of a rotating body is much smaller than the size of a sample (for example.. the validity of the NewtonStokes rheological equation for many real liquids. R a radius of cylinder. . the value of K is found from a calibration experiment in which the torque and angular velocity are measured for a liquid with known viscosity. and in particular.e. If this apparatus is used for comparative measurement. Velocity distribution in flow of a Newtonian liquid in an infinite volume is expressed by the equation V= ωR 2 r [5. Numerous experiments were carried out to confirm theoretical predictions on the relationship of torque. K. the value of a geometrical factor. All of them demonstrated good correlation between theory and experimental results in limits of a laminar flow. i.28] where ωis an angular velocity of cylinder rotation. Eq 5. and geometrical sizes of rotating bodies. is found from the sizes of instrument elements.140 Rheological viscous fluids K= R2 − R2 o i 4πHR 2 R 2 o i When a rotational viscometer is used as an instrument for absolute measurements. Then Eq 5. The rotation of a cylinder in an infinite volume is an interesting limiting case (Ro∴χ4 ∞).
Then coordinates of the boundary parallel planes are +H/2 and H/2. Let the shear stress at an inner cylinder be calculated in usual manner as σi = M 2πR i H [5. stress at any point of a material exceeds the yield point. which can be written as σ = σw − ∆P y L [5..e. we have a situation when a solid (nonfluid) layer exists near an outer cylinder (up to the value of a radius where shear stress becomes equal to yield stress). Malkin 141 It is interesting to investigate the situation when a gap between cylinders is filled with viscoplastic liquid. and this solid layer rotates together with an outer cylinder. If this condition is not valid.30] It is convenient to draw a coordinate system in such a manner that the plane y = 0 would coincide with a middle section of a gap (plane of symmetry).16. (ii) Flow under pressure. Let us assume that both boundary surfaces are motionless and flow between planes along the yaxis is provoked by the pressure gradient gradP = ∆P/L.A. The shear stress profile is given by Eq 5.29] and shear stress at an outer cylinder is σ o = σ i α 1 It is evident that σo <σi The whole volume of a material flows if σo > σy i. Ya. It is easy to understand that the flow through a channel is symmetrical and .
The first case (flow of a Newtonian liquid) is the simplest case. cases. It looks like this: V(y) = − H 2 ∆P [1 − (2β) 2 ] 8η L [5. which means that σw = ∆P L [5. and maximal at the wall.31.3. have a linear profile. Profile of shear stresses shear stress leads to linear change of shear in flow between two parallel planes rate only for a Newtonian liquid. If dV/dy = 0. The velocity profile must be different because linear change in Figure 5. Figure 5. The linear profile of stress is automatically reflected by a linear profile of shear rate and thus a parabolic profile of velocity.e.32] The “minus” sign before the righthand side of this equation shows that flow occurs in a direction opposite to the gradient of pressure. The last two conclusions (existence of the maximum in velocity profile at the axis of a stream and linear profile of shear stresses) are valid for any liquid. and β is a dimensionless distance from the axis of a channel: β = y/H.3..4 demonstrates three typical situations: • velocity profiles for Newtonian liquid (a) • nonNewtonian liquid (b) • viscoplastic liquid (c). . shown in Figure 5.142 Rheological viscous fluids dv = 0 at y = 0 dy i. as calculated from Eq 5. velocity profiles for “rheological” liquids will be nonlinear. the velocity profile has a maximum at the middle plane (or at y = 0). in all other under pressure gradient.31] The shear stresses. The shear stress is zero at the axis of a stream. then shear stress also equals zero.
A. Malkin 143 Figure 5.34] BH 2 It is useful to introduce a value of the average velocity. Ya. nonNewtonian (b). Vo. volumetric output divided by the area of the crosssection.33] Shear rate profile and the value of the shear rate at the wall (maximal shear rate) can be calculated as often required in applications. The volumetric output in the flow of a Newtonian liquid under a pressure gradient is expressed in the following manner: Q= − BH 3 ∆P 12η L [5. determined as & γo = Vo = Q BH i. Velocity profiles for Newtonian (a).e. and viscoplastic (c) liquids in flow under pressure. especially in the theory of viscometry: 6Q [5.4.. Then Vo = − H 2 ∆P 12η L .
This relationship can be written as follows dV σ= K dy n1 dV dy where K and n are constants of the rheological equation and the segment written before rate of shear can be treated as apparent viscosity depending on shear rate. First of all. though its value at the axis is zero as before. Then the velocity profile becomes nonparabolic (but with the maximum at the axis of a stream). . equals V max = 3 Vo 2 Now. Vmax. L.35] where V* is dimensionless velocity.144 Rheological viscous fluids It is interesting to note that the maximal velocity at the axis of a channel. it can be calculated as ∆P = 12ηV o L H2 [5. Finally. which must be created to produce some average velocity of a stream in a plane tube of the length.36] Let us carry out a similar analysis for nonNewtonian liquids. Let us assume that the rheological properties of a liquid are expressed by a power law often used in the theory of polymer processing. if pressure. we can see that nonlinear relationship between shear stress and shear rate results in the rate of shear profile. we can write the equation for the velocity distribution in a dimensionless form V* ≡ V 3 = [1 − (2β) 2 ] Vo 2 [5. is of interest.
can be expressed through the corresponding value of a Newtonian liquid & γw = 2n + 1 & γo 3n . these relationships take the form of the abovewritten expressions for a Newtonian liquid. Ya. although it does not give useful information. Two points are of particular interest. because shear stress is also zero. Malkin 145 Such “power” liquid velocity profile is expressed by the equation n ∆P n H V(y) = n + 1 KL 2 1 n+1 n n+1 1 − 2β n [5. with all the evident consequences of this phenomenon. Shear rate profile is easily calculated as a derivative of velocity. the rheological effects cause modification in the velocity profile.A. The second point is much more interesting. The first is the zero value at the axis. in flow of a “power” liquid. therefore. giving a quite trivial relationship between these variables.37] where β = y/H as before. We can calculate shear stress at this point according to Eq 5. It is a point at the wall. Maximal velocity (at the axis of a channel) is V max n H = n + 1 2 n+1 n ∆P n KL 1 and it is easy to find an average velocity Vo = 1+ n V max 1+ 2n For n = 1.31 to find shear rate at the wall as & γw = 2(2n + 1)Q nBH 2 [5.38] Shear rate at a wall.
(iii) Superposition.31. It is then possible to construct a flow curve “pointbypoint”. it is important to understand velocity profiles. In some applications (for example. i. If shear stress at the wall and layers near the wall exceed the yield point.. n n [5.e.146 Rheological viscous fluids & where the value γ o is calculated from Eq 5. no movement through a channel occurs. For the Newtonian liquid. when flow is generated by superposition of drag due to the movement of a boundary plane and pressure gradient.34. changing volumetric output or pressure gradient and thus changing shear rate and shear stress. the linear relationship exists between volume output and pressure gradient. and the velocity profile appears as shown in Figure 5. in theoretical analysis of processing of polymeric materials in extruders). calculated from Eq 5. then flow becomes possible in this layer but not in the central zone of a channel. the same relationship is also true and n = 1. If the shear stress at the wall. Let us now discuss the main peculiarities of flow of viscoplastic liquid in a plane channel under pressure. is lower than the yield stress.40] . and the material behaves like a solid body. The relationship between pressure drop and volumetric output in flow of a “power” liquid is given by: 2n + 1 Qn ∆P = 2 n+1 LB K 2n+1 H n It is evident that the last equation can be written as ∆P = K n Q n where Kn is the geometrical factor which is evidently calculated as 2n + 1 LB K n = 2 n+1 2n+1 n H It is worth mentioning that the powertype relationship between pressure gradient and volume output reflects the power law for the relationship between shear stress and shear rate.39] [5. and observe superposition of effects discussed above.4c.
The existence of the drag component of flow is proven by the nonzero value of velocity at the upper boundary plane.5.e. Velocity profiles in flow of a Newtonian liquid between two parallel planes when there is superposition of drag and flow under pressure: (a) exit closed. The first is a reflection of drag flow. Such analysis is easy for a Newtonian liquid because we can simply summarize velocity profiles for both components of a stream. The left picture illustrates a very interesting situation when an exit is closed so that the net output is zero.41] where β = y/H is a dimensionless coordinate. In this case. Malkin 147 Figure 5. The right picture represents typical superposition of drag and pressure streams oriented in the same direction.5.41 contains two members. as before. The same is true for integral characteristics of flow. i. volumetric output: . illustrating velocity profiles. Ya. It is quite evident that Eq 5. and the second represents flow under a pressure gradient. It means that output created by drag of a boundary plane is compensated by negative (or “back”) flow under pressure. Now.A. (b) pure drag flow. The middle picture shows a pure drag flow. the areas between velocity profile and a vertical (zero) line are equal on positive and negative sides. The result of calculations in dimensionless variables is as follows: V(y) β − 3β(1 − β)H 3 ∆P = Vw 6η V w L [5. let us analyze an analytical expression for velocity profiles in superposition of drag and pressure flow. is shown in Figure 5. (c) superposition of drag and pressure flow.. The general picture.
. If a flowing liquid is characterized by nonNewtonian properties. characteristic pictures drawn in Figure 5. B. high pressures can appear only for highly viscous liquids) and velocity of a moving boundary plane. as an arithmetic sum of drag and pressure outputs cal . Then. Moreover. and the second originates from existence of a pressure gradient along a channel.148 Rheological viscous fluids Q= V w H H 3 ∆P − 2 12η L [5. and volume output due to drag. Again.43] ξ≡ P = Q D 6η V w L Two particular cases are of primary interest: at ξ = 1. We can introduce a value of volume output due to pressure gradient. QP. we see that volume output consists of two components: the first is related to drag flow. the method of calculation of net output. That is why in discussion of Figure 5. All other cases reflect superposition of both factors and their relative “weight” is determined by the value of ξ. Depending on rheological character of liquid. QD. It is especially interesting to separate the case of zero output represented by the left picture in Figure 5. Besides. output is zero (the exit is closed) at ξ = 0. a dimensionless ratio is a measure of mutual inputs of pressure and drag: Q H 2 ∆P [5. there is a pure drag flow and pressure gradient is absent. This pressure is ∆P = 6V w η H2 L The structure of this equation demonstrates that the pressure created is proportional to the viscosity of a liquid (i. the analytical expressions for velocity profiles and output must be modified. we can calculate the pressure created by a movement of a boundary plane.5 are also valid.42). the general physical idea of superposition of drag and pressure flow remains valid. If Q = 0.5.42] (the width of a channel.e. is omitted from both members of Eq 5.5 we did not mention what “rheological” kind of a liquid it represents.
It appears necessary to solve the balance equations for any new type of rheological liquid and analyze a solution on an individual basis. which has been used above. In flow of a Newtonian liquid through a channel.A. such as transport of oil and oil products. It is often called the Poisseuille problem. under pressure gradient. Such solutions are not of general value. with a round crosssection. the geometrical factor is K= πR 4 8η L and the solution of the Poisseuille problem is the very wellknown HagenPoisseuille equation: Q= πR 4 ∆P 8η L [5.44] . and many others.This discussion concentrates on the situation when the crosssection of a tube is circular with a radius.40 and for a Newtonian liquid (n = 1) Q = K∆P The value of the geometrical factor. depends on the form of a crosssection of a channel.4). The importance of this problem is determined by the fact that flow in straight tubes is a very realistic model for numerous applications. We can immediately state that the relationship between pressure gradient and volume output is expressed by Eq 5. is a classical hydrodynamic problem. pumping water in city networks. Ya.3 FLOW THROUGH STRAIGHT TUBES UNDER PRESSURE Flow through a straight channel (tube). Malkin 149 culated separately. There is no simple method for calculating inputs of both components. though Poisseuille himself studied flow in channels with round crosssection only. K. The example of flow through straight tubes under a pressure gradient has been already discussed in the case of flow between two parallel plates (Figure 5. may become invalid. with arbitrarily chosen crosssection. R. 5.5. which is the main point in discussion of superposition of drag and pressure flow of nonNewtonian liquids.
The first of them is quite evident: velocity profile is symmetrical and shear rate at the axis is zero.N = 4Q πR3 [5.150 Rheological viscous fluids An equation for a velocity profile in the flow of a Newtonian liquid is given by v(r) = 1 ∆P 2 (R − r 2 ) 4η L [5. Two points are of particular interest.45] where r is a current radius. The shear rate at the wall is & γ w. Vmax. The average velocity Vo is Q R 2 ∆P = πR 2 8η L Since the pressure gradient is proportional to flow output.47] . it is easy to write the velocity distribution along a radius through output: Vo ≡ v(r) = 2Q (R 2 − r 2 ) 4 πR The velocity profile is parabolic and the maximal velocity. at the axis of a tube is V max = ∆PR 2 2Q = = 2V o 4 η L πR 2 [5. The velocity profile is known and thus it is possible to calculate shear rate distribution along a radius.46] Velocity profile can be written in dimensionless form v V max = v = (1 − β 2 ) 2V o where β = r/R is a dimensionless radius of a tube. The second point is a position at the wall of a channel.
Malkin 151 Shear stress distribution along a radius is the same as in a parallel plate configuration.Stokes definition: ∆PR 4 [5. It is quite natural that. Linear relationship between output and pressure gradient. we arrive at the geometrical factor for flow of a Newtonian liquid between two parallel plates.A. if a cross section of a tube is not round but elliptical the geometrical factor is η= K el = 1 πa 3 b3 4 ηL a 2 + b 2 where a and b are semiaxes of an ellipsis.50 is the Hagen . The next example is flow through a gap between two coaxial round tubes along the axis. i. linear: σ= ∆P (R − r) = σ w (1 − β) 2L [5. Ya. Let the radii of the tubes be Ro for an outer tube and Ri for an inner tube .48] where σw is shear stress at the wall of a tube: σw = ∆PR 2L [5. in flow of a Newtonian liquid through straight tubes.e. It is also interesting that. Eq 5. which is widely used for measuring viscosity of various liquids determined from the ratio of pressure gradient to volume output if geometrical sizes of a channel (its radius and length) are known. if a = b the factor Kel becomes the geometrical factor for a round tube.49] It is evident that the ratio of shear stress to shear rate calculated at the same point (at the wall of a channel) is indeed the viscosity based on Newton . For example. is of a general nature. if a → ∞ and b = H/2.50] 8QL In fact.. only geometrical factor is varying.Poisseuille equation.
we have the following velocity profile n v(r) = R n+ 1 Then. They also can be found experimentally for model or real channels.40 is always valid. in this case. The situation becomes more complicated for nonNewtonian liquids because the geometrical factor depends on the kind of a rheological equation of state used for calculation. The geometrical factors are also calculated and their analytical forms are known for channels with different regular crosssections. for a channel formed by two round tubes with shifted axes. we return to the flow through a tube with a round crosssection. In flow of a “power” liquid through a straight channel with a round crosssection. V max n = R n+ 1 1+n n 1+ n n 1 1+ n 1 ∆P n n r n K 1.152 Rheological viscous fluids and β = Ri/Ro. Moreover analytical expressions of geometrical factors can be obtained for a channel of an arbitrary crosssection without special problems by means of computer calculations. The geometrical factor for a Newtonian liquid. for example for rectangular or triangle channel. we arrive at the boundary cases: if Ri = 0. R 2L K  1 n ∆P n 2L 1 . is Kc = πR 4 (1 − β 2 ) 2 o (1 − β 4 ) − 8η L ln(1 β) Again. and so on. These solutions are represented by infinite sums of different structure and they will not be reproduced here only because they are too bulky. let us discuss relationships for a “power” liquid bearing in mind that Eq 5. As an example. And if the gap is very narrow and β → 1. we arrive at flow between two parallel plates.
the last equation transits to the above discussed equation for a Newtonian liquid.A. can be found as a ratio of shear stress to shear rate at the same point .e..Poisseuille equation and apparent viscosity is constant. This is also true for all relationships obtained for a “power” liquid. In this case. N 4 [5. wall shear rate for a “power” liquid is related to the corresponding value calculated for a Newtonian liquid in accordance to Eq 5.vs .pressure gradient for a “power” liquid is calculated from the following equation: . Apparent viscosity of a nonNewtonian liquid..52 allows one to construct the flow curve. calculated by volume output. i. Analogous equations can be obtained for different nonNewtonian liquids but in real practice only “power” liquid flow curves are used for applications.52] In the case of n = 1.47. calculated from pressure gradient. Malkin 153 and the average velocity is related to the maximal velocity by Vo = 1+ n V max 3+ n If n = 1. it is not true because apparent viscosity becomes shear rate or pressure dependent. In this case Eq 5. Eq 5. Ya.at the wall: η= ∆P πR 4 1 2(3 + n) L Q [5. Volume output .40 is used as a basic equation.e. η. ∆P n n Q= R 1 + 3n K n 1+ 3n 2L The equation used in the theory of capillary viscometry is an expression for shear rate at the wall: 1 1 1 & γw = 3+ n & γ w.51] i. to find the dependence of apparent viscosity and shear rate. and the geometrical factors are calcu . this equation transits to the Hagen . or shear stress. For a nonNewtonian liquid.
e. The other. and it is the same for any crosssection of a straight channel. The solution of the hydrodynamic problem for a viscoplastic liquid is known as the Buckingham . when σw > σy If this condition is fulfilled. This pattern has been already shown in Figure 5.. The flow of a viscoplastic liquid through a tube occurs only when shear stress at the wall (maximal shear stress existing in a material) exceeds the yield stress.Reiner equation Q= πR 4 ∆P 4 1 4 1 − 3 β + 3 β 8η p L [5. Volume output in movement of a viscoplastic liquid is a sum of two components .53] where β= σw σy . similar to Chapter 4 (Eq 4. at an axis of a symmetrical tube. thoroughly investigated by many authors. in movement of a viscoplastic liquid through a tube. very important case.7).4c. is a flow of viscoplastic. in the form & γ= 1 (σ − σ y ) ηp which has correct meaning when σ > σ y . there is twozone pattern: flowing layer near a wall and nondeformable pluglike zone around an axis. It means that.154 Rheological viscous fluids lated or found experimentally for channels of a different crosssection. a flow occurs in a layer adjacent to wall. i.flow through a nearwall ring and plug movement at the central zone. Let us write onedimensional rheological equation of state of a viscoplastic liquid. It is clear that. nonNewtonian liquid. the shear stress is zero and there is central zone near the axis where stresses are always lower than the yield stress.
If we have the movement of a viscoplastic liquid. N = σw = ∆PR πR 4 & .A. . for example if β < 0.55] Values of shear stress and shear rate measured at the same point (at a wall) can be used for constructing flow curves of viscoplastic liquids. Malkin 155 The equation is written in the form of the classical Hagen .5 is σw = 4 & σ y + η p γ w. γ w. in movement of a viscoplastic liquid. it can be done using the following equation & & γ w.53: Q≈ πR 4 4 1 − β 8η p 3 The structure of Eq 5.Poisseuille equation (item in the front of the square brackets) and a correction term (inside the square brackets). Ya. is to be found. N = 2L 8η p σw ηp [5. then it is possible to use the approximate form of Eq 5. N 3 If the real shear rate at a wall. N − 3(1 − β) 3 − 4β + β 4 [5. under sufficiently high pressure gradient with developed flow zone.54] Another form of the last equation for β < 0. which reflects the effect of plasticity. VP = γ w.53 allows one to rewrite it with variables used for a Newtonian liquid using shear stress and shear rate values related to a wall: 4 1 4 1 − 3 β + 3 β where as before & γ w.5.
and an outer cylinder. In this sense they are close to the drag flow discussed above.6c. Ro. radii of an inner cylinder. In the general case. i.e. Ri. Let us discuss the situation shown in Figure 5. if the gap is not small we meet with a new problem. are functions of the coordinate z. the shape of both bodies (a penetrating body and a vessel) can be quite arbitrary. It is possible to separate three main cases: • flow of a liquid between two coaxial cylinders along their walls . The general similarity of all three cases is that they are all drag flows originating from the movement of solid borders.Figure 5.6b.5. However. The velocity distribution in flow of a Newtonian liquid between two cylinders as in Figure 5.6b • penetration of a solid body into an infinite ”sea" .Figure 5.6c is described by the equation v(r) = (V i + V o )lnr lnR o Ri Ri − Vi [5. for example.. for example transportation of greases through tubes or their work in bearings.4 PENETRATION OF A CYLINDER INTO A VISCOUS MEDIUM The penetration of a symmetrical hard (solid) body into a viscous medium is a model of numerous real applications. 5. two cases are possible: a penetrating body has a sharp top or a flat bottom of the radius R.156 Rheological viscous fluids Many other solutions of different hydrodynamic problems are known for viscoplastic liquids. and so on. directed along the axis of cylinders: Ri(z) and Ro(z). displacement of sealants. the technology of metal rolling. In . Analytical solutions of these hydrodynamic problems are used for various applications related to practical use of such materials. Their main feature is the existence of a nondeformable plug in a zone where stresses are lower than the yield stress in onedimensional flows or its invariant analogue in multidimensional deformation pattern. It is especially evident in the first case.56] Certainly it is very easy to change this equation for changing directions of movement of both cylinders or to analyze the case when one of the cylinders is not moving ( Vo or Vi is zero). moving auger in a soil or oil layer. designing pumping devices for paints. because if the gap between cylinders is small we arrive at flow of a liquid between two parallel planes.Figure 5. stamping of plastic materials.6a • penetration of a solid body into a vessel with a bottom . and so on. Then.
Ya. The first component is absent if Ri is constant. then it begins to sink into a liquid forcing a liquid up to a gap. a penetrating body touches a surface.pressure on the side surface of a penetrating body. The second component is absent if a penetrating body has a sharp top and R = 0. (c) penetration of a cylinder into an unlimited volume.A. At the initial moment. i. Ff. if a penetrating body is a straight cylinder of a constant radius. this value is also a sum of two components . Different types of penetration of a cylinder into a liquid: (a) relative movement of two coaxial cylinders.2. and the distance from the top of a penetrating body to the bottom of a vessel is l. Fp. so we can treat the flow as unidimensional.. The main parameter of interest in this problem is the resistance force F which must be applied in order to push a penetrating body into a viscous liquid.1. Malkin 157 Figure 5. The height of a layer is H.6. the latter case Ri(z = 0) = R. and pressure acting on the flat bottom. The velocity of a movement of a penetrant is V and is assumed to be constant. R. This value consists of two components: • due to viscous friction along the side surface of a penetrating body. • due to pressure acting onto the penetrating body Fp. it can be found if we know shear stresses on the surface. Let us assume that the gap between a penetrating body and an outer vessel is small. (b) penetration of a cylinder into a vessel (both having arbitrary but symmetric shape).e. both values are changing in time. . Fp. proportional to sinking of a body into a liquid.
the shape of a penetrating body and a vessel are known. Let us analyze the problem for a Newtonian liquid. we can calculate all components of the resistance force. In order to find Ff. and they are known because in analysis of any real problem. it is not too complicated: V z (r) = − V lnr lnR i Ro 2 2 1 ∂p 2 R i lnr R o − R o lnr + r − lnR i R o R o 4 η ∂z Ri [5. originated from pressure acting onto the side surface of a solid body Fp. The general solution for the velocity distribution in flow between cylinders is known. is calculated as .58] Now. The pressure distribution is p(z) = − 4 ηV ∫ z dz (R + R )lnR o 2 o 2 i H R i − (R 2 − R i2 ) o [5.57] where r is a current radius. The pressure gradient enters Eq 5. at r = R i (z) dr Then we can calculate shear friction component of resistance Ff = 2πηV ∫ 0 H (R 2 − R 2 )dz o i (R 2 + R 2 )lnR o o i R i − (R 2 − R 2 ) o i [5.57 and it must be found independently. we need to know shear stresses at the solid surface.59] The integral can be easily calculated if both functions Ri(z) and Ro(z) are known. The component of the resistance. Certainly both depend on rheological properties of a liquid.velocity and pressure distributions.158 Rheological viscous fluids All conclusions concerning resistance force can be made if we know two characteristics of the flow . It looks rather bulky though.1. They are found from dv σ = η z. in fact.
58. If R = 0 (a penetrating body has a sharp top) this component of the resistance force is absent.60] where p(z) is pressure distribution given by Eq 5.64] .1 ≈ 12πηV ∫ ∫ Ri 3 dz δ 0 0 [5.A. Ya.62] Resistance due to pressure on the side surface: H H R i dz dR i dz Fp. An interesting and important case is a narrow gap between two cylinders: δ = R o − R i << R i In this case all above written formulas can be simplified and the approximate relationships are as follows.63] Resistance due to pressure on the bottom of a penetrating body: H 3 R 4 R i dz Fp.1 = 0 if dRi(z)/dz = 0. Malkin 159 Fp. as has been mentioned above. Certainly.2 ≈ πηV 3 + 6R 2 ∫ δ3 0 2 l [5.61] where R is a radius of a flat bottom. it is seen that Fp. The component of the resistance. Resistance due to shear friction force: Ff ≈ 6πηV ∫ 0 H R2 i δ2 dz [5. due to pressure acting on the bottom of a penetrating body is calculated as 3 R4 dz Fp.1 = 2π ∫ p(z)R i (z) 0 H dR i dz dz [5.2 = πηV 3 + 4πηVR 2 ∫ 2 2 2 l R i − (R 2 − R 2 ) 0 (R o + R i )lnR o o i H [5.
but it is clear that the role of pressure acting on a bottom of a penetrating body increases when the body approaches the bottom of a vessel. calculating forces in hot stamping of metals and plastics when a puncheon is pressing in a liquid medium during a technological process.e.7). The velocity of penetration is constant and equal to V. the flow of a liquid is twodimensional and the component of velocity vz depends on two coordinates y and z. It is also reasonable to think that Ff < Fp. it describes penetration of a solid body into infinite liquid medium. In this case we have: Ri = R = const and Ro = const. as in Figure 5. In this case Fp.65] This solution of the hydrodynamic problem under discussion can be used for designing dampers. Let us assume that Ro . We may analyze this problem for the case when a penetrating body is a thin flat plane (Figure 5. Let us consider the situation when a round cylinder is penetrating into a cylindrical vessel.62 . It can be analyzed quantitatively based on Eqs 6.6c. i. The solution of the problem regarding the velocity distribution in a liquid medium is known: . on the contrary to the above discussed.. the gap between cylinders is narrow. ξ.6. and obtain R H ≈ 1+ ξ 2δ The final expression for the resistance force is as follows R 3 2Rξ F ≈ πηVR3 + 4 3 2 δ (l o − ξ ) [5. and it depends the depth of penetration of a body into a liquid besides all other factors concerned.2. Then. the following equation allows one to calculate the resistance force 3 R 4 6R3 H F ≈ πηV 2 l3 + δ 3 We can introduce the depth of penetration. If an outer cylinder is absent.66] [5.64.160 Rheological viscous fluids It is rather evident that the relative impact of all these components on a net resistance force differs.R << R. In this case.1 = 0.
can be found.6c .A.. The analytical solution of this problem is known and can be found in textbooks on hydrodynamics. i.67] where ρ is density of a liquid and Erf(x) is an error function determined by the equation Erf(x) = 2 π 1 2 ∫e 0 x α 2 dα Shear stresses. H. for a thin plane penetrating into a viscous Newtonian liquid and the depth of penetration.7. are Figure 5.penetration of a cylinder into an infinite medium . Malkin 1 y V 2 v z (y. the final expression for the resistance force.68] The situation included in Figure 5. In fact. for example in oil industry. real rheological properties of a medium must be taken into consideration. the soil can be treated as a Newtonian liquid and the known solutions can be applied to this problem only as the first approximation. those of a soil and an oil layer. the following equation is valid: ηρHV 3 F = 4B π 1 2 [5. considering two sides of plane. σw ηV ∂v = η z = V πzρ ∂y y = 0 1 2 Now.can also be analyzed theoretically.z) = − V 1 − Erf zηρ 2 161 [5. It is worth saying that the last problem is very important for penetration of a tube into different media. Ya. at the surface of a plane. . F. Penetration of a thin plane into a liquid medium. For a plane of the width B. In this case.e.
is usually used. M. which allows one to neglect the edge effects (the socalled von Karman problem).70] where Ω is the rate of rotation. Cmf.8 Re 0. followed by the same formal operations which have been utilized in analyzing the problem for a Newtonian liquid.71] where the Reynolds Number for the problem under discussion is expressed as . Detailed calculations of the rate of shear field and then a torque give the following result M = 11. is determined for a Newtonian liquid as R ∂V ϕ M = 4πη∫ r 2 dr 0 ∂z z=0 [5. The torque. for example.162 Rheological viscous fluids The solution of this problem can be reached if a proper description of the rheological properties of a medium is used. and V ϕ is a circular component of the velocity vector.5 [5. 5.69] where zcoordinate axis is oriented normal to the surface of a disc.5. R. for mixing a liquid by rotation of an agitator. and ρ density. Then. the dimensionless coefficient of viscous friction.5 It is necessary to find the resistance to a rotation as a function of its speed and R. This problem is a model for many real technological operations.5 RESISTANCE TO ROTATION OF A THIN DISK IN A LIQUID Let a thin disk rotate in a viscous fluid around its axis.8R 4 ηρΩ 3 ( ) 1 4 [5. In the theory of mixing (agitation). rcoordinate axis coincides with the radius of a disc. it is easy to demonstrate that the dependence of this coefficient on the dimensionless characteristic Reynolds Number is C mf = 1. The width of a disc is much smaller than its radius.
71 needs to be modified without changing its structure. rate of flow. The expression for the Reynolds Number reflects nonNewtonian properties of a liquid. Nevertheless. it can be rather different if we take into account the edge effect and some other details.8. Eq 5. The value of the numerical coefficient in Eq 5.8).71 can be different than the 1. In fact. At Re < Re* (in laminar flow). where Re* is the critical value of the Reynolds Number corresponding to laminartoturbulent transition. The exact value depends on the rheological properties of a real liquid and can be found theoretically and/or experimentally for a real situation of torque resistance during rotation of a disk in various “rheological” liquids. two limitations must be remembered: • Eq 5. Eq 5.71 is valid for laminar flow only • Eq 5. Dependence of the coefficient of viscous friction in rotaFigure 5. Meanwhile.8 obtained for a Newtonian liquid. In transition to the turbulent zone at Re > Re*.71 is found for a Newtonian liquid.8 resembles Figure 4.71 is a good approximation and gives results close to experimental data. and indeed tion of a thin disc inside a liquid on it represents the same phenomenon of the dethe Reynolds Number: transition from a laminar (I) to turbulent (II) pendence of hydrodynamic resistance on the zone.A.18. Eq 5. Malkin 163 Re = R 2Ωρ η The numerical value of the coefficient in Eq 5. For nonNewtonian flow. Transition to turbulent flow changes the law of resistance. . Figure 5.71 is a result of approximate solution of the hydrodynamic problem. Ya. It can be representative if we consider the dependence of the dimensionless coefficient of viscous friction on the Reynolds Number in logarithmic coordinates (Figure 5. as in the case of a powertype liquid discussed above. the viscous resistance has larger effect than predicted by this equation (dotted line in the range of Re > Re*).71 is obeyed.
One of the interesting results of the theory of diverging flow of a Newtonian liquid in a diffusor is proof of the fact that a pure converging flow can exist only for sufficiently small angles.9. That is: • flow through a cone channel • flow in a channel formed by two flat inclined planes.channels with increasing crosssections) is a rather standard situation in different technological apparatuses and transportation pipes. but two cases are of main interest to model real situations.5. For nonNewtonian liquids. where definitions of coordinate axes are given in a cylindrical coordinate system. In all other cases. as shown in Figure 5. and confusors . The solution of a hydrodynamic problem of a Newtonian liquid flow is Figure 5. Scheme of flow between two known. this problem was thoroughly studied theoretically. which is radial velocity. and velocity profile and pressure gradient can be calculated for any particular case.9. It is expressed in the form of elliptic functions.channels with decreasing crosssection. Basic diagram of flow in a flat diffusor6 is shown in Figure 5. and the velocity profile is symmetrical to the plane α = 0.164 Rheological viscous fluids 5. and exact solutions are known for Newtonian liquids only. and one can find it in textbooks flat inclined planes. The cylindrical coordinate system is shown. solutions for “rheological” liquids are found by numerical methods. Therefore. We can assume that there is only one nonzero component of velocity. a solution of the problem of converging (or diverging) flow can be analyzed by computer methods only.9. Velocity equals zero at the walls. or . α o .6 CONVERGING (DIVERGING) FLOWS Converging (or diverging) flows take place when a crosssection of a channel is changing along its axis. The size of a crosssection can be quite arbitrary. on hydrodynamics. Flow in channels with changing crosssection (diffusors .
and Eq 5. zones with backstreams appear. the velocity profile at each crosssection (determined for r = const) is parabolic.. In the opposite case. Ya.α ) = 3 Q α 1 − 2 Bα o r α o 2 [5.73] So. Malkin 165 α o < α max [5. velocity profile can be calculated as V(r.72 is not obeyed. B width of a channel (in the direction perpendicular to the plane of a drawing). It is quite an expected result. For the problem under discussion Re = Qρ rαV o = Bη Bη where Q is volume output. These zones can exist near walls. a simple approximate relationship takes place: α max ≈ 10. for slightly diverging flat tubes. i.73 is very similar to the wellknown HavenPoisseuille solution for flow of a Newtonian liquid through a flat tube. though it is rather complex. Vo average velocity. In the situation when an angle α o is very small.A.e.e. the value of α max is small. and r and α are current coordinates. If the condition 5.2 Re i. The exact analytical solution for α max is known. or zones with direct and back streams can alternate.72] where 2α max is some critical value of the angle between plates and it depends on the Reynolds number. For Re > 1 (in the limits of laminar flow). but it is important to emphasize that it is valid only for very small values of α o . velocity profiles appear .. and the number of such zones depends on Re. Re.
and Q is a volume output. .166 Rheological viscous fluids to be nonparabolic. where the origin is at the apex of a cone (Figure 5. manner: p −po = 1 ηQ(1 − 3γ 2 ) − 1 2 r3 r3 π(1 − γ o ) (2γ o + 1) o [5.10. ro is a radius of the edge cross section. Again. the size of this layer is proportional to (Re)1/2. The flow is symmetrical in respect to the axis of a cone and two components of velocity Vr and V α are present. In the first approximation (when only the older member of the series is preserved). It is convenient to analyze the problem in a spherical coordinate system. and then viscous effects are negligible. we come to the interesting result: velocity profile appears almost flat for the main part of crosssection of a channel. the solutions of hydrodynamic (balance) equations are known in the form of a series only. where r is radial. pressure distribution in flow through a round cone Figure 5.74] where γ = cos α and α is a current angle calculated from an axis of a cone. The general approach to the theory of flow in conical diverging (converging) channels is very similar to the analysis of flow in a flat channel with changing cross section. and α angular coordinates. According to the theory. In this case.10). and only near walls is there an abrupt decrease of velocity up to zero at the walls. γ o = cosα o . is a current radius of a diffusor. channel is represented in the following The spherical coordinate system is shown. Flow in a cone channel. Even for a Newtonian liquid. Let us consider some peculiarities of flow in converging channels (confusors). r. po is pressure in this section. simple analysis can be done for Re > 1. It means that viscous resistance occurs in a very thin (narrow) layer near the walls. This fact is the base for the theory of a boundary layer which explores the general ideas: effects of viscous resistance to flow are important only at short distances from the solid surfaces. where α o is an angle between a solid wall of a cone and its axis.
r.74. must be linear and can be expressed by an equation Q= K ∆P η where ∆P is the pressure drop providing volumetric output. this relationship is expected to be . the relationship between pressure drop and volumetric output will appear nonlinear. one can find a simpler equation for K. If we consider a conical channel as a sum of round channels of the length dl. for a Newtonian liquid. which can be found in standard textbooks on hydrodynamics. Along the way we shall find the following result K= R3 R3 3π 1 2 2 2 8L R1 + R1 R 2 + R 2 2 2 where R1 is a radius of a conical channel at the entrance. The exact expression for K is rather complex. it seems reasonable to summarize pressure drops. but for low viscosity liquids. such as polymer melts or crude oils.A. The pressure drop is proportional to the volumetric output and this is a feature typical for Newtonian liquids. we can think that the relationship between volumetric output and pressure drop.74. In a general case. based on the following arguments. dp. Malkin 167 The preservation of the first member of a series for p(r) is valid for viscous liquids when their viscosity is sufficiently high. However. This values can be calculated from the HagenPoisseuille equation. it is necessary to utilize the full solution of a problem. for a Newtonian liquid having viscosity. However. R2 is a radius of a conical channel at the exit. Ya. and K is the geometrical factor depending on the size of a channel. and the first approximation can be found from Eq 5. This is true for many liquids. Indeed. We can expect that for “rheological” liquids. Q. η. this result is not adequate for the rigorous solution expressed by the known series or even its first approximation represented by Eq 5. with changing radius. and L is the length of a channel (between radii R1 and R2). for a powertype liquid. resulting in the expression for ∆P. for all segments of a channel.
dl. Again. a liquid able to store large deformation in the course of flow) through a conical channel. the central zone will be motionless. It is clear that the radius of this pluglike zone is changing along its length. special case is a flow of an elastic liquid (i. V o.2 = 2 πR1 πR 2 2 It means that the flow in a conical channel is accelerating and an extensional gradient of velocities appears. as in flow in cylindrical channels. The gradient of velocity equals & ε= V o. If a liquid is viscoplastic.e. can be calculated theoretically from the solution of a balance equation.2 L and the extension ratio is R λ= 1 R 2 2 Flow of an elastic liquid in a conical channel leads to uniaxial extension.1 and Vo. Let the radius of a conical channel be changing along its length from R1 to R2.1 − V o.2. and stresses are less than yield stress near the axis.1 = Q Q . A very interesting.. and its characteristics can be found using the last two equations. because shear stress at the axis is absent. we can calculate average velocities at entrance and exit sections Vo. Extension of an elastic liquid in its flow through a conical channel can be effectively used for creation of an orientation which is fixed beyond the exit section of . bearing in mind that the volume output is constant. it seems that calculating K(n) and summarizing pressure drop in cylindrical segments of a channel of the length. Then. can lead to inadequate results. K(n).168 Rheological viscous fluids Q = K (n) ( ∆P) n where the geometrical factor. They are V o.
when the problem nite volume (a) or inside a vessel (b). This idea is a basis for the technological operation which is utilized in production of highstrength and highmodulus polymeric filaments. The first is a steady movement of a solid body in unlimited (infinite) volume (see Figure 5. That is the reason why calculation of a resistance to movement of solid bodies through a viscous liquid is a very important problem met in different applications.11a). the force. solid walls are absent or placed so far from a moving ball that their influence is negligible.11b) where the influence of walls on the hydrodynamic situation must be taken into account. Movement of a spherical ball in an inficussed above.5. Fs. In this case. Ya.7 Two cases are possible and are considered in theory. 5.11. The second case is a movement of a solid body in a vessel (Figure 5. Malkin 169 a channel. of penetrating a symmetric body into a symmetric vessel was analyzed. The latter case is close to the situation disFigure 5. necessary to support the steady movement of a ball in a Newtonian liquid is calculated as Fs = 6πηRV [5.A. A moving body does not need to have a spherical shape but a defined geometrical shape instead. According to a wellknown solution by Stokes. and is known as the Stokes problem. The simplest of them is the process of sedimentation of solid particles due to gravitational forces. It is a model of various bodies moving in a sea (submarines and many others).7 MOVEMENT OF A BALL THROUGH A VISCOUS FLUID The hydrodynamic problem of calculating the force required for a sphere to move through a viscous liquid was first analyzed by Stokes.75] . A solid ball moving through a viscous liquid is a very popular model of numerous real situations.
is calculated as a difference between weight of a ball and hydrostatic flotation force: P= 4 πR3 g(ρ s − ρ 1 ) 3 [5.e.76 are equal.170 Rheological viscous fluids where R is a radius of a ball (sphere). According to Goldstein’s calculations. In the steady movement. Further analysis shows that this solution is valid at low Reynolds Numbers calculated as Re = 2RVρ η where ρ is density of a liquid. ρ s density of a moving solid body. It was shown that influence of inertial forces (i.1. the exact formula for resistance to movement of a ball. In this situation.77] . transition to situations when Re is not small) can be analyzed using correction factors. is as follows 3 19 F = Fs 1+ Re − Re 2 + K 16 1280 where FS is the Stokes force calculated from Eq 5.75 and P calculated from Eq 5. Fs calculated from Eq 5. It is evident that the second member in the brackets (linear correction term) can be neglected in comparison with 1 when the Reynolds Number is of the order of 0. The movement of a ball due to gravitational forces is of special interest. when Re is not small. and then we can find the velocity of steady movement ρ − ρ1 2 V = gR 2 s η 9 [5.75. ρ 1 density of a liquid. V velocity of the steady movement. P..76] where g is the gravitation constant. the moving force.
It is quite evident that η= 2 gR 2 (ρ s − ρ 1 ) 9 V [5.78] This formula can be used only with the following limitations: • it is valid for steady movement of a ball • it is possible to neglect the influence of walls of a vessel • rheological properties of a liquid are described by the NewtonStokes Law • movement of a ball is rather slow and Re < 0. Then V=− 1 gρR 2 3 η [5. 5.1. and ηo its viscosity. Eq 5. Ya. Theoretical calculations show that in this case the velocity of steady movement can be calculated as9 V= 2 g(ρ o − ρ 1 )R 2 η + ηo η 3 2η + 3η o [5.77 for a solid ball moving in a viscous liquid. Another limiting case is connected with the assumption that ηo << η. we may apply Eq 5.77. calculated according to the Stokes formula. for example.80] .79] where ρ o is density of a liquid ball.A. The second member in the brackets is a correction factor for inertial effects. the case of a gas bubble in a viscous liquid. and inertial effects must be taken into consideration. It is evident that if ηo → ∞. Eq. If movement of a ball is not very slow. Malkin 171 If velocity is measured and densities of a solid ball and liquid are known. A very special modification of the Stokes problem is related to the situation when a moving ball is not a solid but liquid and its viscosity is ηo . the equation for viscosity calculation must be modified: 27 V 2 ρ 1 η = ηs 1 − 16 gR ρ s − ρ 1 where ηs is viscosity.77 can be used to determine viscosity of a Newtonian liquid.
For example.172 Rheological viscous fluids The “minus" sign. it is preferable and more reliable to find values of K experimentally or on the basis of some empirical formulas.79 and 5. the resistance to movement of a ball can be written as F = KηV where K is a geometrical factor.80 can be used for practical applications in different technological problems related to liquidliquid separation. and so on. and in such case. moving in a Newtonian liquid) also can be investigated by methods of theoretical hydrodynamics which allow us to establish values of the geometrical factor. and a disc is moving in the direction perpendicular to its plane. if a moving body is a thin disk of a radius. i. For a spherical body K = 6πR For solid bodies of various shapes. is used. degassing. R= .. the same equation. Sometimes. shows that a gas bubble moves in a direction opposite to the positive coordinate axis. then 16a 9π Other situations (for example. R means some geometrical parameter. ellipsoids. as for a sphere. R. Both Eqs 5.81] If this disk is moving along its plane. Eq 5.81 seems to stay valid but the problem of calculation of the geometrical factor is quite independent and requires separate theoretical or experimental determination.e. then R= 8a 3π [5. submarines). and so on. Nevertheless. Then. Eq 5. in the last equation. for a Newtonian liquid. especially for bodies of complicated geometrical shape (for example.77 is a linear relationship between velocity and reciprocal viscosity. in practice. up rather than down as in former cases. cylinders.
the introduction of corrections is necessary. Malkin 173 It is also useful to have a formula for calculation of stress field around a moving ball. If a liquid is nonNewtonian. and only in some special cases.77 for viscosity must be modified by adding a correction factor. It acts at the surface of a ball and can be found as σ max = R (ρ s − ρ 1 )g 3 [5. the dependence of the resistance to movement. can be expressed by the power equation F = K (n) V n where K(n) is a geometrical factor. Simple final expressions are absent.01. and n an exponent in a power law (of the rheological equation of state). The most important value is the maximum shear stress.104 R o R + 2. let us consider what happens if a ball moves. It is easily seen that corrections become comparable with 1 at (R/Ro) > 0. F. According to the wellknown calculations by FaxenLadenburg. in many practical cases. The complete stress distribution can be calculated but the solution is rather complex. but in a vessel where the influence of its walls cannot be neglected. for example. is it reasonable to neglect the influence of the walls of a vessel. but we can think that.77). the resistance force can be found by numerical solution of hydrodynamic equations with an appropriate constitutive equation. viscosity of a Newtonian liquid is expressed as8 R η = ηs 1 − 2. not in infinite liquid space. Eq 5. Theoretical analysis shows that in this case.95 R o 2 4 where Ro is a radius of an outer cylinder (tube) along which a ball is moving and ηs is viscosity calculated from the Stokes equation (5.A. as before. V. if a ball is falling in a cylindrical tube. Ya. for a “power law” liquid. . Then.82] Now.09 R o R − 0. at velocity.
to σ = 0 in various coordinate systems used to determine “zeroshear” Newtonian viscosity. If a liquid is viscoplastic. results of determination of apparent viscosity depend on a driving force. Newtonian viscosity is found by extrapolation of η(σ ) dependence to σ = 0 in coordinates η1 − σ 2 . 5.82 exceeds yield stress. we can assume that in the range of relatively low shear stress. Then.174 Rheological viscous fluids In application to shearrate dependent viscosity. v z << v r . The method of extrapolation can be rather arbitrary. Other methods of extrapolation.10 There are peculiarities of flow under discussion. i.e. or shear stress.12). a ball can move through such a medium) only if maximal shear stress calculated from Eq 5. then it can flow (i.82.5.. a medium behaves as a solid and it is irrelevant to consider resistance to the movement of a ball. Shear stress is calculated from Eq 5. can also be found in the literature. The liquid layer is compressed because of bringing the plates together (Figure 5. This problem was first analyzed by Reynolds.8 COMPRESSION OF A LIQUID BETWEEN TWO PARALLEL DISKS Let a Newtonian liquid be placed between two parallel round plates (discs).e. the dependence of apparent viscosity on shear stress is expressed as η= ηo 1+ Aσ 2 where ηo is maximum (“zeroshear”) Newtonian viscosity and A is constant. For example. as follows: • It is reasonable to assume that the radial component of velocity dominates. In the opposite case. This limiting “zero” apparent viscosity can be treated as a quite reliable value of maximum Newtonian viscosity. In this case the following procedure is useful: it is necessary to make measurements and calculate apparent viscosity at different shear stresses and then extrapolate experimental data to “zero” conditions (zero shear stress or zero shear rate).
and vr = 0 where h is the distance between parallel plates.12. Let the velocity of the upper plate. is linearly decreasing with time because v= dh dt . vz = V = const. Ya. h. • Inertial forces are neglected. we analyze the case of relatively low values of the Reynolds Number. • flow generated by a constant force applied to the upper plate.12). at V = const. V.A. let us consider the situation when a liquid completely fills the space between disks and when they are approaching each other the surplus of a liquid squeezes out the gap and does not take part in further consideration. It is evident that. be known. Compression of a liquid layer the axis passing through the center between two parallel plates (discs) squeezof the disks. the distance between disks. • The flow is symmetrical in respect to Figure 5. Two different basic cases are of primary interest: • flow induced by the preset constant velocity of the upper plate moving down: at z = h. i. ing out a liquid from the gap. Then.e. we would like to know • time dependence of the force which resists approaching the disks and must be applied in order to support movement • velocity and pressure profiles. First. so the volume of a liquid in the gap decreases with time.. Malkin 175 and besides ∂v r ∂v << z ∂r ∂z (orientation of the axes is shown in Figure 5.
h [5. The integral of p(r) along the radius gives the full force. required to create movement with constant velocity F= 3πηVR 4 3h3 [5. and po is pressure at the outer free surface.85] [5. at r = R. F. and h grows (at V = const) linear to time.87] The resistance to approaching plates increases with h3. These results show why it is so difficult to squeeze out a .84] Pressure distribution along the radius is p = po + 3η V (1 − ζ 2 ) 3 2 h R [5.86] where ζ = r/R is a dimensionless radius.176 Rheological viscous fluids The solution of the problem under discussion for velocity distribution is vr = 1 ∂p 2 (z − hz) 2η ∂r [5.83] and we need to know pressure distribution 6ηv ∂p =− 3r ∂r h finally we have vr = 3α ( γ − γ 2 ) V where dimensionless sizes are used: α= r z γ= h.
in the case of constant volume of a liquid droplet. if a liquid is not only viscous but viscoelastic (see Chapter 7). we wish to compress a small liquid drop.. and a very thin film of a liquid always stays in a gap. respectively. i. i. when a liquid is squeezed out the gap. the resistance force increases with h5. In this situation the resistance force is calculated as 3πηVR 4h 2 o o F= h5 and. liquid from narrow gaps pressing solid boundary surfaces: when the distance between surfaces.A.13. If a liquid placed between plates is nonNewtonian. is preset. However. Compressing of a liquid between two parallel plates when a liquid stays in the gap. The results of theoretical calculations discussed above are widely used in the rubber industry. There are some standard methods to characterize raw materials by their behavior in compression between parallel plates (in socalled compression plastometers). which again demonstrates how difficult it is to squeeze out a liquid from a narrow gap. even faster than in the former case. . Let us now discuss the situation when the size of discs is large and a liquid stays in the gap between discs (Figure 5. the force grows rapidly up to unlimitedly high values. but not a velocity.e. resistance force. Ya. and so on. In this case the condition of constant liquid volume is valid πR 2h o = πR 2h o where Ro and ho are initial radius and height of a liquid droplet.13). h. becomes very small. Malkin 177 Figure 5. These methods are particularly convenient for such highly viscous liquids as raw rubbers. the general solution does not exist. The form of these formulas depends on the accepted rheological equation of state of a liquid. the movement of an upper plate becomes slower and slower when discs are approaching each other because of increasing resistance to flow in a narrow gap.. and R and h are current (timedependent) values of the droplet sizes. it is not very difficult to make all necessary calculations and find all analogous formulas for velocity and pressure distribution. When a compressing force.e.
industrial greases are very often viscoplastic and/or viscoelastic liquids. with the driving force for this movement being the rotation of the rolls.9 HYDRODYNAMICS OF ROLLING The situation shown in Figure 5. because it is easy to imagine that a thin layer of a solidlike material will stay in the gap between solid surfaces.178 Rheological viscous fluids Perhaps the main application of the flow of a liquid between compressing plates is related to understanding the performance characteristics of greases in sliding bearings. δ. The main characteristic parameter of the stream is the outstripping factor. Model of rolling. stretching wires. 5. we shall cite some reFigure 5. However.11 Let a flat slab (strip) of a viscous or viscoplastic liquid pass through the gap between two rolls. H and h being much less than the radius of the rolls. and so on. sults primarily related to flow of a Newtonian liquid.14. and this problem successfully models the main peculiarities of grease performance. That is why this model was investigated for different rheological liquids. it requires rigorous analysis of the complete hydrodynamic problem with an appropriate rheological equation of state. R.14 is a model of many industrial applications including rolling of metal slabs. and when quantitative characteristics of their performance are of interest. In this case. In order to give an idea about main peculiarities of the model. processing of plastics and rubber compounds.5. The initial width of a strip is 2H and the width of a gap is 2h. taking into account plasticity of a liquid is especially important. determined as δ= Q −Qo Qo . and this circumstance prevents the contact of sliding bodies.
calculated via α . F. Theory also gives formulas for pressure distribution along the surface of rolls. The results were obtained by either analytical or finite element analysis methods and can be used to design . There are a lot of publications devoted to calculations of the dependencies of the force. Ya. and power consumption in roll rotation. which moves rolls apart. and Q is a real quantity of a material passing through a gap between the rolls: Q = 2∫ v x dy 0 h [5. on geometrical sizes of an apparatus and rheological properties of a material for nonNewtonian and viscoplastic liquids. ω is angular velocity (frequency of rotation). But in fact (and experiments confirm it) the δfactor depends on rheological properties of liquid and can be distinguished from the values calculated using Eq 5. F can be expressed by a linear relationship: F = Kηω where K is a geometrical factor. F. net force. β. Theoretical calculations give the following approximate expression for the δfactor in rolling of a Newtonian liquid: δ= α −1 5 1 2 1+ 2αβ 1 − α + α α+ 1 6 3 [5. This is true for a Newtonian liquid.A. and R.89.89] whereα = H/h andβ= h/R are dimensionless geometrical parameters andβ<< 1. It appears that the δfactor is completely determined by geometrical sizes of the apparatus used. Malkin 179 where Qo is an apparent quantity of a material which would pass through the gap if a material is solidlike and moves with the circumferential velocity of the rolls: Q o = 2ωRBh where B is the length of the rolls.88] vx is a velocity component directed along the xaxis. For a Newtonian liquid.
Vi is a speed at the surface of a bob (Vi = ωRi). it is a development of a theory of flow between two round cylinders when eccentricity (shift in position of axes of cylinders) exists.. but in a tangential movement.13 give the angular distribution of pressure.δ is the average gap between cylinders (δ = Ro . and this force prevents shift of a bob from the common axis and favors its stabilization in rotation.e.90] where Ri is a radius of a bob (inner cylinder or a rotating shaft). Ro is a radius of an outer cylinder.5.15. It is a model of a radial bearing with a lubricant and shift of a bob (rotating shaft) from the common Figure 5.12 One important fact worth mentioning: for “rheological” liquids. modelling deformations of a grease in a gap. we arrive at the main result of the theory of lubrication. Theoretical calculations10. the dependence of F on angular velocity is not linear as for a Newtonian liquid.180 Rheological viscous fluids industrial equipment and determine its technological characteristics. 5. F. This result is a proof that an additional radial supporting force appears.10 FLOW IN A LUBRICANT LAYER This is a rather special but very important case of flow. This force. The final formulas and applied guidelines for calculations can be found elsewhere. layer between two eccentric cylinders. i. as shown in Figure 5. Flow in a lubricating axis can be initiated by a radial force. not in compression (as discussed in previous section). In fact. L is the length of a bob. the distance between axes of inner and outer cylinders. this result is quite analogous to other abovediscussed conclusions for flows of different types when we transit from Newtonian to nonNewtonian liquids. S is the surface of a bearing (S = 2πRiL). ωis frequency of rotation. α is dimensionless eccentricity: α = δ ε and ε is eccentricity.Ri). . is calculated as F= 2 6ηSR i V i α 2 δ (1+ 2α )(α − 1) 2 2 1 2 [5.15. If we integrate this distribution through an angle.
M. M. becomes very small).16: an inclined plate is moving relative to a flat surface.91] There is a correspondence between eccentricity and two main parameters: supporting force.what is more important . Eq 5. F. Flow between a flat surface and a sliding inclined plate. The limiting situation corresponds to the case of α → ∞. The resulting equation is M= ηSV i R i δ 2α (2 + α 2 ) (1+ 2α )(α − 1) 2 2 1 2 [5. at low radial forces or . for a rotating bob. Malkin 181 It is also possible to find the torque.e. Change of the distance between plates is characterized Figure 5.. It means that an increase in rate of rotation really results in stabilization of the position of a bob close to the axis of an outer cylinder. This case can be modeled as shown in Figure 5. ε. Then. eccentricity.. Ya.e.16. by the linear relationship x h = h o 1+ k a 1 .90 can be rewritten as Fδ 2 =γ 6ηSV i R i where γ= α2 (1+ 2α 2 )(α 2 − 1) 2 is a function of eccentricity. and torque.at high velocities of rotation) α grows unlimitedly (i. it can be easily demonstrated that at low values of γ (i.A.
and it is calculated as F= 6ηVBa 2 k 2h 2 o 2k ln(1+ k) − 2 + k [5. and ho is given in Figure 5.2. a lubricating layer can resist pressure and this is the physical reason why a lubricant works. F. but introduction of elasticity leads to many new effects which depend on real properties of a medium (or. . Sliding of a flat plate is a limiting case of the full theory. but the main idea concerning the existence of a supporting force in a lubricant layer is valid for any liquid.16 and k characterizes the inclination of the upper plate. Coordinate axes are also shown in this Figure. x. which corresponds to a slightly forced or very quickly rotating shaft when the eccentricity is small. in fact. also appears. F. In this situation. a supporting force. which acts against the direction of movement (sliding) of an upper plate P= ηVBa 2 kh o 6k 4ln(1+ k) − 2 + k [5. due to the appearance of a supporting force. the majority of lubricants used in industry are “rheological” liquids and the whole theoretical structure built for a Newtonian liquid must be repeated for any other liquid if quantitative results are expected. It is easy to prove that P passes through a maximum at k ≈1.16ηV a 2B h2 o It is also possible to find the resistance force. h. and at this value of k. Therefore no general solution exists. maximal value of the supporting force is Fmax ≈ 0.92] where B is the size of plates in the direction perpendicular to the plane of the drawing. in other words. It is relatively simple for a pure viscous liquid.93] Thus.182 Rheological viscous fluids where the meaning of notations a. P. on the rheological model used). Though the classical theory of lubrication was developed for a Newtonian liquid.
In some cases we cannot be quite sure whether a material is a liquid or not.e. glues.Stokes) liquid. If relaxation takes place much quicker than deformation (or stress) is measured. and so on.e.e. this definition requires estimation of a time factor. Such definition can be based on the idea that liquid is a material which flows. That is why it is correct to consider liquidlike behavior of matter “from an experimental point of view”. liquid is a substance which can flow at infinitesimally small stresses. Therefore. it is reasonable to treat this substance as a liquid. and for a pure liquid. no elastic deformation can exist.A. semiliquid glasses. Moreover. Rheological equation of state (constitutive equation) for any liquid can be formulated either in terms of relationship between invariants of stress and rate of deformation tensors or as energy dissipated as a function of invariants of these tensors. it is not always possible to distinguish between pure viscous and viscoplastic media. or to viscoelastic media. i. they behave as typical liquids. But at stress higher than the yield stress. Ya. for such substances as resins (especially at low temperatures). we need a rigorous definition of a liquid. for example. The level of the yield stress can be very low (infinitesimally small). In this case. such media flow. bitumen.. The position intermediate between solids and liquids is occupied by viscoplastic bodies: they cannot flow up to some limit of stress (yield stress) and at low stress they behave as solidlike bodies.. Malkin 183 5. liquid for which linear relationships between components of stress and rate of deforma . i. This is true.. and that is why. the criterion of yielding for a viscoplastic liquid must be also established in terms of invariants of the stress tensor. Another approach to an idea of flow of a liquid is related to the concept of dissipation of energy supplied to create flow: work done for deformation of a liquid is completely converted to heat (dissipates). in practice. i. which is opposite to deformation of solids. its deformations are irreversible. where work is partly stored. One of the fundamental concepts in rheology is an idea of a Newtonian (or Newton . because development of deformation proceeds in time and always there is a danger that an experimenter did not have enough time to observe any deformations at all.6 CONCLUDING REMARKS In real life we meet with liquids very often. where work is completely stored. However. This is the simplest linear liquid.
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tion tensors exist. The coefficient for this linear relationship is viscosity (or Newtonian viscosity), and according to the definition, viscosity of Newtonian liquids is a material characteristic of a liquid which does not depend on conditions of flow (i.e., on stresses or rates of deformation). Viscosity of a Newtonian liquid can be measured at different geometrical schemes of deformations. As a general rule, the term viscosity is related to shear flow, and this coefficient is a constant of proportionality between shear stress and rate of shear. All other coefficients of viscosity are related to this value. For example, a coefficient between normal stress and rate of extension measured in unidimensional stretching, called Trouton viscosity, is equal to the threefold value of the shear viscosity of this liquid. It means that shear viscosity is a unique material parameter of a Newtonian liquid. However, if a liquid is anisotropic (as liquid crystals), some independent viscosities exist even in a linear model of a liquid, and viscosity appears to be a tensor value by itself. Many real liquids are nonNewtonian. It means that their apparent coefficient of viscosity, determined as a ratio of shear stress to shear rate of deformations, depends on conditions of flow. Various mathematical models of nonNewtonian flow have been proposed, discussed in literature, and used for solving applied problems. Among them, one of the most popular is the socalled “power” liquid. This liquid is characterized by power dependence of shear stress on shear rate. Different mathematical equations are proposed for viscoplastic liquids, too. The simplest of them is the Bingham model. In this model, shear rate is proportional to the difference between current shear stress and the yield stress. But apparent viscosity of the Bingham model is not constant, but rather, is a decreasing function of shear stress. Rheological models of liquids are used by for comparison of different liquids. This comparison can be done for two levels: • different liquids can be distinguished by the constitutive equation which describes their flow properties in the best way • liquids of the same rheological type can be distinguished by the values of material constants which enter these equations as numerical coefficients. The main field of application for rheological equations of state (constitutive equations) is in solving hydrodynamic problems, which are described by balance equations with appropriate boundary conditions.
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To solve a hydrodynamic problem means: • to find space distribution of stresses, velocities, and pressures for a certain volume determined by solid boundaries • to establish relationship between integral force and kinematic parameters of flow, such as pressure drop and output in flow through channels (inner problems) or resistance force and velocity for movement of a solid body through a liquid (outer problems). There is a great variety of hydrodynamic problems because the number of possible configurations of channels through which liquids flow and solid bodies moving inside a liquid is unlimited. But some situations are very typical and are widelyused for modelling real technological and engineering situations. These are: plane unidimensional flow, flow through tubes with different constants and changing crosssection, movement of solid bodies in a liquid, compression of a liquid layer between planes, rotating rolls, and so on. These are only a few examples, and certainly many other hydrodynamic situations exist. For any of them, the hydrodynamic problem can be solved by analytical and/or computer methods. If any of these hydrodynamic situations is analyzed for a Newtonian liquid, we can expect that a linear relationship between integral force (or torque) and kinematic parameters (velocities) takes place. For nonNewtonian liquids, analogous relationships are nonlinear. In the case of viscoplastic media, motionless zones appear in areas where stresses do not exceed yield stress of a material. Some hydrodynamic problems for a Newtonian liquid can be solved analytically; others require applying approximate or computer methods to find solutions. For nonNewtonian liquids, mathematics becomes (as a general rule) too complex to find solution in an analytical form and the methods of computational analysis are used.
5.7 REFERENCES
1. 2. 3. 4. 5. 6. 7. 8. 9. V. G. Kulichikhin and A. Ya. Malkin, Vysokomol. Soed., 21A, 1407 (1979). R. S. Rivlin, Proc. Roy. Soc., A193, 260 (1948). I. Braun and M. Reiner, Quart. J. Mech. Appl. Math., 5, 42 (1952). M. Couette, Ann. chim. phys., 21, 433 (1890). Th. Kármán, Zeitschr. für angew. Math. Mech., 1, 244 (1921). G. Hamal, Jahresber. Deutsch. Math. Ver., 25, 34 (1916). G.G. Stokes, Trans. Camb. Phyl. Soc., 9, 8 (1851). R. Landenburg, Ann. der Phys., 22, 288 (1907); 23, 447 (1907) T. Rybczynski, Bull. Acad. Sci. Cracovie, 40 (1911); J. Hadamar, Comp. Pendus, 152,
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1735 (1911). 10. O. Reynolds, Phys. Trans., 177, 157 (1886). 11. I. V. Meshcherski, Repts. First Petrograd. Polytechn. Inst., 28 (1919). 12. R. E. Gaskell, J. Appl. Mech., 17, 334 (1950); N. Tokita and J. L. White, J. Appl. Polym. Sci., 10, 1011 (1966); I. Brazinsky, J. Appl. Polym. Sci., 14, 2771 (1970). 13. Lord Rayleigh, Phys. Mag., 35, 1 (1918).
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6
ELASTIC SOLIDS
6.1 DEFINITIONS
The concept of an elastic solid is an idealization of the real behavior of numerous materials. Some of them are close to this model − for example, steel and stone. Others are rather far from this ideal model, but in some applications they can also be treated as elastic solids − for example, wood, rubber, and concrete. These examples show that the elastic solid is in fact a concept of behavior rather than a particular material. On the other hand, the same material can behave as a solidlike or liquidlike material, depending on the timescale of observation. Consequently, the type of rheological behavior is determined by the Deborah Number, i.e., the ratio of inner and outer timescales. The basic idea of an elastic solid has already been formulated in Chapter 4. The elastic solids are materials which completely store work of their deformation and return energy after removal of the outer forces. Another approach to the idea of elastic solids can also be advanced. If elastic solids are treated as materials with an unambiguous relationship between stresses and deformations, i.e., if we know the stress field, we know the space distribution of deformations, and vice versa. The main point in both concepts is absence of time or timeeffects. If deformation is timedependent (in a permanent stress field), it is always a characteristic feature of viscous (or dissipative) behavior of matter, though it can be combined with elasticity.
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Elastic solids
The next step in formulating the rheological model of an elastic solid, i.e., in writing its rheological equation of state (or constitutive equation), is a transition from components of stress and deformation tensors observed in any experiment dealing with invariant formulation. It can be an expression for elastic potential (stored energy) as a function of invariants of stress or deformation tensor or both. It can also be a relationship between invariants of stress and deformation tensors. Both approaches work in formulating rheological equation of state, and the result can be reformulated from the energy concept to the components of stressvsdeformation tensors. This transition is based on a fundamental expression for elastic potential (stored energy): dW = ∑
i
∑σ
j
ij
dε ij
[6.1]
Continuing, we arrive at the following evident formula for the stress components calculated from an elastic potential σ ij = ∂W ∂ε ij [6.2]
and if we know W as a function of deformations, then components of the stress tensor can be easily calculated from Eq 6.2. It is also important to have a method of conversion from the stressvsdeformation relationship, written in invariants, to the elastic potential function. W can be written as a function of three invariants: W = W(E1, E2, E3) where E1, E2, and E3 are invariants of the tensor of large deformations. Then using the ordinary rule of differentiating complex functions, we have σ ij =
3 ∂W ∂W ∂E k =∑ ∂ε ij k =1 ∂E k ∂ε ij
[6.3]
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The last equation gives an answer to the problem formulated above: indeed, if a function W(E1, E2, E3) is known, we can calculate components of the stress tensor from Eq 6.3.
6.2 HOOKEAN ELASTIC MATERIAL
The initial formulation of the concept of the Hookean elastic material has been given for uniaxial extension by Eq 1.2. σ E = Eε where E is the elastic (Young) modulus. Sometimes a constant reciprocal to the elastic modulus is also used. This constant is called compliance, I: I= or ε = Iσ E Analogous relationships can be written for other geometrical schemes of deformation. For bulk (volume) compression, we have 1 ε v = p B where ε v is a relative change of volume: εv = ∆V V 1 E
p is hydrostatic pressure and B is bulk modulus of compressibility. Linear elastic behavior in shear is expressed by the equation
one needs to find a different form of invariant description of rheological properties of a linear (Hookean) elastic material. It is also possible to think about other types of deformations (e. Evidently. discussing uniaxial extension. such as σ ij = kε ij [6. and σ is tangential (shear) stress. E.5] where k should be an universal constant characterizing properties of a material. we introduced the values of the Young modulus. and it would be necessary to introduce “moduli” characterizing linear behavior of a material.4] Here ε is shear. reflecting its linear elastic properties in different modes of deformations which would include all these relationships? • what is a minimal number of independent characteristic constants (“moduli”) describing all types of deformation of a material? The first. In Chapter 3. biaxial extension).bulk. shear. Therefore. extension.190 Elastic solids ε= 1 σ G [6. and the Poisson coefficient (ratio). there are many characteristics of linear rheological behavior of a material . and shear are different and this is not reflected in the concept of the linear relationship between corresponding components of stress and deformation tensors • in uniaxial extension..g. But this approach is evidently wrong. . Young moduli. ε 22 and ε 33 (in directions perpendicular to the line of extension) are not zero because an extended body compresses in perpendicular directions. most straightforward attempt to construct the general rheological equation of state for a linear elastic material appears to consist of an assumption of linear relationship between corresponding components of the stress and deformation tensors. G is the shear modulus. Poisson coefficient. but the components of the stress tensor σ22 and σ33 are absent. Indeed: • experiments show that the constant k is not universal because coefficients of linear equations for bulk compression. Then the main questions are: • how to write the general rheological equation of state for such material. and this means that there is no simple correlation between σij and σij. µ.
and these are different and independent effects. . If we recall that hydrostatic pressure p= − I1 3 [6.6] where I1 is the first invariant of the stress tensor (measure of hydrostatic pressure). shape changes of a material. Assuming that linear relationships between spherical and deviatoric parts of both tensors exist separately I1 = kE1 and σ′ ij = 2Gε ′ ij [6. σ′ ij are deviatoric components of the stress tensor.8] then Eq 6. we assume that shape (form) and bulk (volume) changes in deformation are independent phenomena and must be considered separately. and the resistance to shape changes. Ya.7] [6. not only the form but a volume of a body changes. on one hand. In a more general sense. That is why we need to introduce at least two independent constants for complete characterization of resistance of a material to volume changes. the first of them characterizing resistance to volume and the second one. B and G.6 can be rewritten as p = − BE1 where B = k/3 is the bulk modulus of elasticity. The two fundamental coefficients. This recalls the idea of splitting stress and deformation tensors into spherical (isotropic) and deviatoric parts. on the other. and k and G are material constants. Malkin 191 The basic idea of constructing such a description is related to the fact that in uniaxial extension. E1 is the first invariant of the deformation tensor (measure of relative volume changes).A. are sometimes called Lamé factors. ε′ ij are deviatoric components of the deformation tensor.
7 is the shear modulus. ε 11 = and E1 = (1 − 2µ ) σE E σE . ε 22 = ε 33 = − µε 11 E where E is the Young modulus and µ the Poisson ratio.7 with those which are directly measured in a standard experiment .192 Elastic solids The value of G in Eq 6. in uniaxial extension is p = − ∑ σ ii = i σE 3 Then.6 and 6. according to Eq 6.7 are valid for any type of deformation and that they are the invariant definition of a Hookean elastic material (body). It is important to connect the constants in Eqs 6.6. Hydrostatic pressure. as shown in Chapter 3. and the coefficient 2 in Eq 6. Let σ E to be the extensional (normal) stress. Then.7 relates the formal definition of components of the deformation tensor.6 and 6. We can assume that Eqs 6. and discuss the situation in the limits of instantaneous deformations. p.uniaxial extension. we come to the equality σE σ = B(1 − 2µ ) E 3 E and then we have E = 3(1 − 2µ )B This equation also gives us useful information because .
• for known constants E and µ B= E . It is interesting to consider the expression for the bulk modulus via constants E and µ. its volume cannot increase.A. it can only decrease or may not change at all. Ya. if a body is incompressible. 3B+ G µ= 3B − 2G 6B+ 2G • for known G and µ E = 2G(1+ µ ). 3(3G − E) µ= E − 2G 2G B= 2G(1+ µ ) 3(1 − 2µ ) This set of relationships allows one to find any value of a material constant from two other values measured experimentally. Malkin 193 σo E and as a final result σ E = 2G(1+ µ ) E = 2G(1+ µ ) We can now calculate any pair of constants for any pair of variables. It is quite evident that when we compress a body. It is important to note that in a general case there are only two independent constants which need to be measured. It means . • and for known E and G B= EG . as summarized below. 3(1 − 2µ ) G= E 2(1+ µ ) • for known constants B and G E= 9BG .
. and E = 3G It means that for incompressible media there is only one independent or “free” material constant. to think that some materials are completely incompressible. and this inequality can be fulfilled only if µ ≤ 0.5 The particular case of incompressible material is of special interest.194 Elastic solids that there is a principle limitation: B≥0 Then. Let us consider (for the sake of simplicity) an incompressible body. E1 = 0. and W can be a function of E2 and E3 only.. i.9] . The simplest idea is an assumption of linear relationship between W and E2. it is reasonable to accept that B → ∞. Now.e. we can reformulate the rheological equation of state for a linear Hookean elastic material in terms of the elastic potential function. The fact is that for many solids B >> G i.e. It is a good model (or it is almost true) for all liquids and rubbers. Then we have two simple relations µ = 05 . it is much easier to change the shape of a body than its relative volume (density). In some cases. it is also evident that E >0.. [6. i. Then. W = BE2 where B is a material constant.e.
A.e. Though both definitions are equivalen