Journal of Non-Newtonian Fluid Mechanics 187–188 (2012) 8–15

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Journal of Non-Newtonian Fluid Mechanics

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A critical overview of elasto-viscoplastic thixotropic modeling

Paulo R. de Souza Mendes a,⇑, Roney L. Thompson b
a
Department of Mechanical Engineering, Pontifícia Universidade Católica-RJ, Rua Marquês de São Vicente 225, Rio de Janeiro, RJ 22453-900, Brazil
b
LCFT-LMTA-PGMEC, Department of Mechanical Engineering, Universidade Federal Fluminense, Rua Passo da Pátria 156, Niterói, RJ 24210-240, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The literature on thixotropy modeling is reviewed, with particular emphasis on models for yield stress
Received 11 February 2012 materials that possess elasticity. The various possible approaches that have been adopted to model the
Received in revised form 8 June 2012 different facets of the mechanical behavior of this kind of materials are compared and discussed in detail.
Accepted 24 August 2012
An appraisal is given of the advantages and disadvantages of algebraic versus differential stress equa-
Available online 2 September 2012
tions. The thixotropy phenomenon is described as a dynamical system whose equilibrium locus is the
flow curve, and the importance of using the flow curve as an input of the model is emphasized. Different
Keywords:
forms for the evolution equation for the structure parameter are analyzed, and appropriate choices are
Elasticity
Viscoplasticity
indicated to ensure a truthful description of the thixotropy phenomenon.
Thixotropy Ó 2012 Elsevier B.V. All rights reserved.
Modeling

1. General aspects of elasto-viscoplastic thixotropic models
The current status of modeling elasto-viscoplastic thixotropic
materials has achieved a matured stage, as a result of the develop-
ments of important research groups like the ones whose work is ci-
ted in this manuscript. Although there is still a long journey ahead
to reach the goal of predicting this kind of material behavior under
complex motion, at least the viscometric response has achieved a
stage, where a comprehensive critical overview is worth while. In
contrast to the general thixotropic reviews of Mewis [1], Barnes
[2], Mujumdar et al.[3], and Mewis and Wagner [4], the present
text is focused on thixotropic effects in elasto-viscoplastic materi-
als. Hence we are particularly interested in identifying in the liter-
ature and analyzing the approaches that were employed to model
the thixotropic behavior combined with elasticity and plasticity.
The various models available in the literature can be roughly
grouped into two different types. In one of these, which we will call
Type I, the approach starts with a viscoplastic stress equation, to
which elasticity and thixotropy are introduced, following Houska
[5] [e.g. 3,6]. In the other type, here denominated Type II, the ap-
proach starts with a viscoelastic stress equation, to which plasticity
and thixotropy are introduced [e.g. 7,8].
For modeling yield stress materials, in Type II models plasticity
is introduced by using a viscosity function that diverges at high
structuring levels [9,7]. For apparent yield stress fluids, a viscosity
function that possesses a high-viscosity Newtonian plateau in the
low strain-rate limit is employed [10,8,11]. A recent Type II model
⇑ Corresponding author. Tel.: +55 2131141177; fax: +55 2131141165.
E-mail addresses: pmendes@puc-rio.br (P.R. de Souza Mendes), rthompson@
mec.uff.br (R.L. Thompson).
has been proposed that accommodates both true yield stress mate-
rials and apparent yield stress fluids [12].
The most usual way to model thixotropic behavior is to intro-
duce a structure parameter, typically called k, that represents the
level of organization of the material internal microstructure.
The next step is generally to postulate a correlation between the
structure parameter k and bulk properties such as viscosity and
elastic modulus (or yield stress). A common feature of thixotropy
models is to introduce an evolution equation for the structure
parameter to capture the time-dependent behavior of the material.
This is invariably formatted as a kinetic equation, where the com-
petition between a buildup and a breakdown term is represented
[13]. An equilibrium or steady state condition is achieved when
the rates of destruction and of construction of the microstructure
become equal.
2. Type I models
The Bingham model has a very strong influence on the visco-
plasticity literature. Accordingly, a large number of thixotropy
models available in the literature are of Type I, i.e. are based on
the Bingham model, to which other features are added.
The Bingham model clearly arises from the introduction of the
yield stress in the classic Newtonian fluid constitutive model.
The yield stress sy is an entity that traditionally appears in consti-
tutive equations of solid mechanics. When subjected to stress lev-
els below this yield stress, the material has a ‘‘solid-like behavior’’,
and above the yield stress it possesses a ‘‘liquid-like behavior’’.
In the Bingham model, the solid-like and the liquid-like
contributions are combined as additive parts of the total stress s.

0377-0257/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jnnfm.2012.08.006
 P.R. de Souza Mendes, R.L. Thompson / Journal of Non-Newtonian Fluid Mechanics 187–188 (2012) 8–15
Therefore, thinking in terms of a mechanical analog, we can say
that the two contributions are combined ‘‘in parallel.’’ An impor-
tant consequence of this framework is that the viscosity goes to
infinity as the strain rate approaches zero.
The Newtonian fluid contribution may be replaced by a non-
linear function of the strain rate. If this is done, then we get a mod-
ified Bingham model that keeps its essential features. For example,
if a power-law dependence with the strain rate is assumed, then
the Herschel–Bulkley model is obtained. The Herschel–Bulkley
model is perhaps the most representative constitutive relation of
this kind, and also the most used one.
The solid mechanicians usually assume that below the yield
stress the material presents an elastic behavior, which is most of-
ten ignored by the fluid mechanicians when modeling a viscoplas-
tic material. However, it is true that a number of fluid-mechanics
oriented authors proposed ways to add elasticity in a Bingham-like
model.
The most intuitive way to introduce elasticity into a viscoplastic
model was proposed by Oldroyd [14], by replacing the solid contri-
bution, i.e. the behavior below the yield stress, by an expression
that takes the form of a Hookean solid. Thus, the elastic modulus
G—another traditional quantity in solid mechanics—comes into
play. In this case, the resulting constitutive equation is
 rate c_ h ¼ c_  c_ e . In other words, the evolution equation for ce is di-
s ¼ sy þ lp c_ if s P sy
s ¼ Gc if s < sy
where lp is the plastic viscosity, c is the strain, and c_ is the strain
rate. Interestingly, this additional elastic expression creates an
equivalence between the yield stress and a yield strain, the latter
being defined as the deformation that occurs at the yield point, gi-
ven by cy = sy/G.
Thixotropic models of Type I follow Oldroyd’s general idea to
introduce elasticity into the stress equation. In these models, the
features of Eq. (1) are generally expressed in the following single
equation for the stress:
s ¼ Gs ce þ gs c_
In this equation, Gs is a structural elastic modulus, gs is a struc-
tural viscosity, and ce is the elastic strain, i.e. the recoverable part
of the total strain.
Representative elasto-viscoplastic thixotropic models [e.g. 3,6]
originate from Oldroyd’s approach described above. Four ingredi-
ents compose the models of this type: (i) the equation for stress,
(ii) the relation between the material properties and the structure
parameter, (iii) the evolution equation for k, and (iv) an equation
for the evolution of elastic strain ce. The three first ingredients also
appear in Type II models (to be discussed later), while the last
ingredient deserves special attention, due to its crucial role in the
mechanical behavior predicted by Type I models.
The physical reasoning that leads to a specific type of evolution
equation for ce is typically not discussed in enough detail in the lit-
erature, in contrast to the prolific discussions often found to de-
scribe the underlying physics of the other model ingredients. For
example, it is common that the evolution equation for the struc-
ture parameter be described as a competition between a break-
down term and a buildup term. It follows that some general
features arise from this viewpoint which provide guidance to the
construction of a new model. The process of building a specific evo-
lution equation for k is thus reduced to deciding what characteris-
tic thixotropic time will be used, which parameters should be
chosen to appear in the buildup term, what physical quantity is
responsible for the destruction of the material microstructure,
and so on, as it will be discussed later on in this text. There are
no counterparts, clearly stressed in the literature, for the evolution
equation of ce.
9
2.1. Examining Type I models from the viewpoint of mechanical
analogs
It is interesting to analyze Type I models from the mechanical-
analog viewpoint. Note that the existence of some mechanical ana-
log for every model is a requirement of Newton’s second law.
The two additive terms of Eq. (2) imply a mechanical analog
with two branches, one whose stress intensity is gc_ , and the other
whose stress intensity is Gce. Since c  ce, the equation for stress
cannot be translated in to a mechanical analog in a straightforward
manner. There is a need for a description of the mechanism that
rules the deformation c  ce. A possible analog for Type I models
is shown in Fig. 1. This analog possesses a mechanical component
in series with the elastic component Gce. Because, by definition, the
elasticity of the model is given by the elastic component Gce alone,
it is reasonable to infer that this component—indicated by an inter-
rogation mark in Fig. 1—is a viscous mechanism of the form gh c_ h ,
where c_ h ¼ c_  c_ e is its strain rate. The subscript h stands for ‘‘hid-
den,’’ because this component does not appear explicitly in the
formulation.
The presence of this hidden mechanical component is what
makes Eq. (2) different from the one describing a Kelvin–Voigt
material. This hidden mechanical component governs the strain
rectly related to an evolution equation for ch, which in turn is a
ð1Þ
consequence of the physical nature of the hidden mechanical
component.
Next we examine two thixotropic models representative of
Type I under the optics of the mechanical analog shown in Fig. 1.
In these models, like in the vast majority of the models available
in the literature, the structure parameter is defined such that it
varies within the range between 0 and 1; k = 1 indicates the high-
est structuring level, while k = 0 corresponds to the lowest struc-
turing level.
2.1.1. Finding the hidden mechanical component of the model of
Mujumdar et al. [3]
ð2Þ
The stress equation of the thixotropy model proposed by
Mujumdar et al. [3] is summarized below:
s ¼ kGo ce þ ð1  kÞK c_ n ð3Þ
(
c_ e ¼ c_ if jce j < cy ðkÞ ðpre  yieldÞ
ð4Þ
jce j ¼ cy ðkÞ ðpost  yieldÞ
where cy ðkÞ ¼ cy0 km ð5Þ
In the equations above, Go is the structural elastic modulus of
the fully structured material, K is the consistency index, n is the
power-law index, and cy0 is the elastic strain of the fully structured
material.
It is clear that the stress acting at the hidden mechanical com-
ponent is the same as the stress acting at the elastic component. As
discussed earlier in a general context, since there is no elasticity in
Fig. 1. A possible mechanical analog for Type I models.
10 P.R. de Souza Mendes, R.L. Thompson / Journal of Non-Newtonian Fluid Mechanics 187–188 (2012) 8–15

the hidden component, then it is treated as a viscous component. In the case that the structural elastic modulus does not depend
Hence, on the structuring level, then Eq. (12) takes the same form of Eq.
(11), even if the structural viscosity gs is strongly dependent on k.
kGo ce
kGo ce ¼ gh c_ h ) gh ¼ : ð6Þ This fact was explored by several authors [e.g. 19,10,20] to construct
c_ h models in which the polymeric contribution is given by an equation
From Eqs. (4) and (5) we have that of the form of Eq. (11), with the Maxwell viscosity l being replaced
8 with a structural viscosity gs(k). Some of these authors have also
< gh ! 1 ðpre  yieldÞ
added a matrix contribution, and ended up with a Jeffreys-like
kGo cy0 km ð7Þ
: gh ¼ _ m1 dk ðpost  yieldÞ model. Quemada [10] goes a little further and also considers a
cc y0 mk dt
Burger’s-like model. Clearly, all these models are restricted to mate-
Eq. (7) illustrates that the physical nature of the hidden rials whose structural elastic modulus is independent (or at most a
mechanical component of this model is not clear. very weak function) of the structuring level (dGs/dk ’ 0).
One of the few models for elasto-viscoplastic thixotropic mate-
2.1.2. Finding the hidden mechanical component of the model of rials based on Eq. (12) was proposed by Yziquel et al. [7], who
Dullaert and Mewis [6] adopted a full 3D approach by replacing the time derivative with
The stress equation of the thixotropy model proposed by an upper convected one. They also introduced a solvent viscosity
Dullaert and Mewis [6] is summarized by the following equations: to come up with an Oldroyd-B-like equation. An important contri-
bution of this work is a comparison between different origins of
s ¼ kGo ce þ ðkgs0 þ g1 Þc_ ð8Þ structure destruction. This aspect is discussed in more detail
 b below.
k
c_ e ¼ 4 ½sðk; c_ Þcy0  seq ðc_ Þce  ð9Þ A recent model of Type II was proposed by de Souza Mendes
t
[8,11]. In these works, a novel assumption has lead to a
where gs0 is the structural viscosity of the fully structured material, Maxwell-like [8] or Oldroyd-B-like [11] stress equation, with no
g1 is the viscosity of the material at the lowest possible structuring restrictions regarding the dependence of the structural elastic
level, t is the time, seq ðc_ Þ is the equilibrium (steady-state) stress cor- modulus on the structuring level.
responding to c_ , and k4 and b are constant parameters. The two parts of this assumption can be summarized as follows.
Following the same procedure that we used above for the model Firstly, a neutral configuration is introduced, represented by the
of Mujumdar et al. [3], we can determine the hidden mechanical neutral elastic strain cen. All configurations are defined with re-
component for the model of Dullaert and Mewis [6]. The following spect to any arbitrary but fixed reference configuration. This neu-
expression for the hidden viscosity gh is obtained: tral configuration corresponds to a state of zero elastic stress,
kGo ce and hence the elastic stress is computed as
gh ¼  b
k4
c_  t
½Go ce cy0 ðk  keq Þ þ gs0 c_ ðkcy0  keq ce Þ þ g1 c_ ðcy0  ce Þ se ¼ Gðce  cen Þ: ð13Þ
ð10Þ The second part of the assumption consists of postulating that
the neutral configuration changes if and only if the structuring le-
where keq is the equilibrium (steady-state) value of the structure
vel changes, which leads to
parameter corresponding to c_ . Thus, the physical nature of the hid-
den mechanical component of this model is even more complex.
1 dGs dk
c_ en ¼ ðc  cen Þ ð14Þ
Gs dk dt e
3. Type II models
Eq. (14) says that the neutral configuration remains unchanged
Another approach for developing the stress equation for an in three (non-exclusive) cases: (i) when the elastic modulus does
elasto-viscoplastic thixotropic model is to start from a viscoelastic not depend on the structuring level; (ii) when the structuring level
model for the stress equation. In this case, the Maxwell model— is not changing, or (iii) when the present configuration coincides
the most fundamental of the viscoelastic constitutive with the neutral configuration, even if the structuring level is
equations—plays the counterpart of the Bingham model when changing.
the goal is to combine solid-like and liquid-like behaviors. Instead Note that, in all the other models mentioned above, the exis-
of combining plasticity with viscous effects, the Maxwell model tence of a neutral configuration that depends on the structuring le-
combines elasticity with viscous effects. In this case, the mechan- vel has not been given the deserved attention. It is well known that
ical analog that represents the combined effects consists of a this issue plays a major role in the description of the mechanical
spring and a dashpot in series, and the resulting equation is well behavior of the type of materials of interest in this text [21–
known: 23,8,11], and neglecting this fact is expected to lead to unphysical
l predictions.
s þ s_ ¼ lc_ : ð11Þ To illustrate this, let us imagine an elasto-viscoplastic thixotro-
G
pic material that is initially fully structured, stress-free and at rest.
where l is the Maxwell viscosity. The way of introducing plasticity At time t = 0, it is subjected to a very high stress which is main-
and thixotropic effects is inspired in the series of papers by tained for a long time, such as to bring its structuring to the lowest
Marrucci et al. [15], and Acierno et al. [16–18], who deal with level, corresponding to a state of no elasticity and low viscosity.
viscoelastic models for non-dilute regimes, where entanglement be- Then, the material is brought to rest. A gradual buildup of the
tween the macromolecules has a significant role on the mechanical microstructure is then observed, and, during this process the mate-
response. If the parameters of the Maxwell model are assumed to rial is expected to remain at rest and stress-free. After a long en-
depend on the structure parameter k, the following constitutive ough period of time, the material initial condition of fully
equation is obtained: structured, stress-free and at rest is expected to be achieved. If
" # the neutral configuration issue is not treated appropriately, how-
gs ðkÞ dGs dk gs ðkÞ _
s 1 þ s ¼ gs ðkÞc_ : ð12Þ ever, a stress buildup may be predicted during the just described
Gs ðkÞ2 dk dt Gs ðkÞ
microstructure buildup process [e.g. 3].
 P.R. de Souza Mendes, R.L. Thompson / Journal of Non-Newtonian Fluid Mechanics 187–188 (2012) 8–15
Type II models also require additional equations to relate the
structural viscosity and the structural elastic modulus to the struc-
ture parameter, and also an evolution equation for the structure
parameter itself. However, Type II models do not need an addi-
tional evolution equation or rule for ce, in contrast to Type I mod-
els, because this information is already embedded in their stress
equation. This additional information is needed by Type I models
because their stress equation does not provide it; it is exactly this
information that is needed to fully construct their mechanical ana-
log (see Eqs. (7) and (10)).
In conclusion, models of Type II are capable of predicting elastic
and thixotropic behavior, and plasticity is readily introduced by
expressing the bulk parameters as functions of the structuring le-
vel such that the structural viscosity is unbounded when the mate-
rial is fully structured [19,7,12].
4. Comparing the stress equations of Type I and Type II models
It is not difficult to observe that the stress equations of Type II
models can be represented by the mechanical analog shown in
Fig. 2. In contrast to what was observed in Type I models, the infor-
mation contained in the analog is fully contained in the stress
equation.
If g1 is set to zero, then the analog reduces to Maxwell-like
form. Note that g1 is the viscosity of the material corresponding
to its lowest structuring level, and hence setting it to zero repre-
sents a rather unphysical assumption that is hardly defensible in
a constitutive model that intends to possess a broad range of
applicability.
From the mechanical analog viewpoint, the main difference be-
tween the two types of models is the way that the structure-
dependent mechanical elements are arranged in the analog. In
Type I models, the mechanical element related to the structural
viscosity and the one related to the structural elastic modulus ap-
pear in parallel, while in Type II models they are arranged in series.
Hence, in Type II models the structure-dependent mechanical ele-
ments are subjected to the same stress level, while in Type I mod-
els they are subjected to neither the same stress nor the same
strain rate.
It is important to notice that these differences lead to opposite
responses to changes of the structural elastic modulus and struc-
tural viscosity. When the elastic mechanical element is in parallel
with the viscous one, the elastic modulus and the viscosity act as
enhancers of elasticity and dissipative behavior, respectively. On
the other hand, when they are combined in series, the elastic mod-
ulus and viscosity act as inhibitors of elasticity and viscous effects,
respectively. In other words, as the characteristic time g/G ? 1, a
purely viscous behavior is obtained when the elastic and viscous
elements are in parallel, and a purely elastic behavior is obtained
when they are arranged in series. When g/G ? 0, the trends are
of course reversed.
The importance of this fact cannot be overemphasized, since in
the literature it is rather common to find the interchangeable usage
Fig. 2. The mechanical analog for Type II models.
11
of the terms ‘‘increasing elasticity’’ and ‘‘increasing elastic modu-
lus’’, which is not always correct. The increase of the elastic mod-
ulus represents an increase on the stiffness only, which by itself is
not determinant of the level of elasticity, as discussed in the previ-
ous paragraph. This misunderstanding is certainly responsible for
the fact that, with rare exceptions [8,11], most Type II models em-
ploy expressions for the structuring-level-dependent elastic modu-
lus that, in the limit of zero elasticity, go to zero instead of infinity.
A striking consequence of the opposite trends of the analog
arrangements discussed above is that the Type I models do not re-
duce to their inelastic counterpart in the limit of zero elasticity, as
it would be expected. In other words, in the framework of Type I
models, in applications, where elasticity is not considered, the
yielding term is just a structuring-level-dependent yield stress,
while when elasticity is considered the yield stress is written as
Gsce. Note that, in the case of Type I models, the limit of zero elas-
ticity implies a null elastic modulus (Gs ? 0). Thus the resulting
model in this limit is at most a thixotropic model with no yield
stress, because both the yield stress and elasticity appear in the
same term. Fig. 1 may be useful to further illustrate this point.
Therefore, a clear inconsistency arises at low elasticity levels. This
is a major limitation that indicates that the main hypotheses
adopted by Type I models are not representative of the underlying
physics of the phenomena involved.
On the other hand, Type II models reduce nicely to inelastic
viscoplastic thixotropic models in the limit of zero elasticity
(G ? 1), as readily inferred from Fig. 2. This is so because the yield
stress effects appear in the structural viscosity (which diverges at
high structuring levels), being thus decoupled from the elastic
terms. Thus it can be concluded that the in-series analog consti-
tutes a more truthful representation of the microstructure
mechanical behavior of these systems.
Mewis and Wagner [4] analyzed some aspects of models of
Type II when compared to models of Type I. Regarding the model-
ing of elasto-viscoplastic thixotropic behavior, in their general
discussion they clearly recommend models of Type I. The argu-
ments invoked to support such preference are expressed in
sentences like ‘‘close link between thixotropy and yield stress,’’
and ‘‘nearly all thixotropic materials have a yield stress.’’ These
statements intend to justify the fact that, in the formulation of
all Type I models, most of the dependence on the structuring level
enters the formulation in the term of the stress equation that
resembles a yield stress.
They also state that ‘‘The lack of a yield stress is a serious draw-
back of the models derived from the Maxwell model,’’ but in the
sequence they mention that it is possible to eliminate this limita-
tion by using a structural viscosity that diverges at high structuring
levels.
Their ultimate argument in favor of Type I models and against
Type II models is now quoted: ‘‘It should be pointed out that a con-
stant yield stress precludes any flow below that value. As discussed
above this is not consistent with the available experimental evi-
dence that suggests that yielding should depend on the shear his-
tory.’’ It is important to observe that this argument is flawed
because it is a circular argument.
The reason is that the mentioned experimental evidence is ana-
lyzed under the optics of the Type I model paradigm. In other
words, to conclude that yielding should depend on the shear his-
tory implies the prior assumption that the correct stress equation
is the one adopted in Type I models, where most of the burden
of describing thixotropy falls on the yield-stress-like term. Under
the optics of Type II models, in which formulation most of the
dependence on the structuring level is introduced in the structural
viscosity, the above quoted argument would not make sense, be-
cause yielding in the classical sense does not depend on shear his-
tory, as discussed in the next section.
12 P.R. de Souza Mendes, R.L. Thompson / Journal of Non-Newtonian Fluid Mechanics 187–188 (2012) 8–15

5. Comments on yielding As a final comment on equations of the type of Eq. (15)—which,

as mentioned above, originate from the classic Herschel–Bulkley
The yield stress sy was firstly introduced as a steady-state flow flow curve—it is interesting to observe that the flow curve corre-
concept, being defined as the stress below which no unrecoverable sponding to these equations is not the Herschel–Bulkley one, inas-
deformation is observed. It is thus a single fixed parameter of the much as sy, K, and n will be functions of the shear rate:
flow curve, and below the yield stress there is no steady state flow
(c_ ¼ 0 in the flow curve). It is simply given by
s ¼ sy ðkeq ðc_ ÞÞ þ Kðkeq ðc_ ÞÞc_ nðkeq ðc_ ÞÞ ð17Þ
sy ¼ limt!1 ½limc_ !0 sðc_ ; tÞ. The yield stress is also the minimum where keq ðc_ Þ is the structural parameter under equilibrium (steady-
stress required to trigger a major microstructure breakdown in state) conditions (see Eq. (19) below for an example of keq ðc_ Þ). Con-
an initially fully-structured material. It is thus a quantity related sequently, the thixotropy models that employ stress equations like
to the fully structured state only. Eq. (15) do not reduce to the Herschel–Bulkley equation as thixot-
Hence, to use the term yield stress to denote a quantity that is a ropy becomes negligible. This important fact is not discussed in
function of the structuring level is clearly not consistent with the the literature, and, actually, flow curve equations are seldom given
concept of yield stress. This inconsistency is commented by Mewis explicitly.
and Wagner [4]: ‘‘It could be argued on physical grounds that
attributing a Bingham yield stress to a structure that exists during
6. The role of the flow curve in thixotropy modeling
flow is not suitable. In practice it is often found to be adequate
parameter to fit constant k curves.’’
6.1. General aspects
As discussed earlier, the strategy usually employed by the most
representative Type I models in order to incorporate thixotropy ef-
Some theories for predicting the behavior of microstructured
fects is to modify a classical flow curve expression by introducing
liquids are developed with basis on features of the microstructure
the dependence on the structure parameter. Taking the Herschel–
and its interactions with the main flow. Other theories are based
Bulkley equation as an example, the idea is to allow the flow curve
on mechanical analogs.
parameters to depend on the structuring level:
The resulting model is then checked with respect to its ability to
predict the trends observed experimentally in different flow situa-
s ¼ sy ðkÞ þ KðkÞc_ nðkÞ ð15Þ tions, including steady shear flow and other rheological flows. If
the trends are correct, then the model parameters can in principle
It is worth noting that, in most applications that use this type of
be determined, acquiring the status of properties of the material.
equation [e.g. 24], K and n are taken as constants, so that the
In the case of thixotropy modeling, an alternate approach for
dependence on the structuring level appears in the first RHS term
developing a constitutive theory is to use the flow curve as an in-
(sy(k)) only.
put for the model [8,11]. Since this curve can in principle be ob-
The underlying physics of Eq. (15) is not clear. Due to the histor-
tained in laboratory, it is a material property that contains
ical use of the symbol sy in association with the yield stress, one is
valuable information about the material behavior in shear, being
readily invited to interpret sy(k) as a yield stress that depends on
analogous to the viscosity of the Newtonian fluids. Hence, to use
the structure parameter. And in fact this is the usual interpretation
this information in the construction of the model seems to be a
in a vast majority of articles. However, while the classic Herschel–
natural choice.
Bulkley equation represents a flow curve, Eq. (15) does not. Actu-
A similar approach was used by Schunk and Scriven [25] and
ally, Eq. (15) represents a family of curves parametrized by k (see
others [e.g. 26–30] in the context of predicting viscoelastic behav-
Barnes [2] and Fig. 4 therein). ior in complex flows.
The flow curve is the relation between stress (or viscosity)
One immediate advantage of this approach is the obvious fact
and strain rate that is observed in steady flow. Each point of that the flow curve is predicted exactly. Other advantages are dis-
the flow curve is associated with a different value of k, i.e. a dif-
cussed in detail in the following sections. It will be shown that the
ferent structuring level. Therefore, the flow curve is intercepted importance and convenience of using the flow curve as an input for
by each and every curve obtained from equations of the type
a thixotropy model cannot be overemphasized.
of Eq. (15). This means that, if an equation such as Eq. (15) is
employed, then there will be a different value of sy(k) associated
with each point of the flow curve, even in the range of very high
strain rates. While the material is flowing, no yielding process—
i.e. dramatic change in the microstructure—occurs that could
possibly justify interpreting sy(k) as a yield stress. Therefore it
becomes quite clear that the only resemblance between sy(k)
and the concept of yield stress originates from the form of
Eq. (15).
It is worth emphasizing that the discussion above is directed to-
wards physical meaning and nomenclature issues only. There is no
implication regarding the appropriateness of employing stress
equations of the form of Eq. (15). A straightforward way to pre-
serve the concept of yield stress and to preclude further nomencla-
ture confusions is to use different symbols to denote the structure
dependent parameter in Eq. (15):

sðk; c_ Þ ¼ AðkÞ þ BðkÞc_ CðkÞ : ð16Þ

The parameter A(k) is given by AðkÞ ¼ limc_ !0 sðk; c_ Þ, and it

should be seen just as a convenient quantity for fitting constant k
curves, as suggested by Mewis and Wagner [4]. Fig. 3. The flow curve as the equilibrium locus of the dynamical thixotropic system.
 P.R. de Souza Mendes, R.L. Thompson / Journal of Non-Newtonian Fluid Mechanics 187–188 (2012) 8–15
6.2. The flow curve as the set of all attractor points
The flow curve is the equilibrium locus of the dynamical thixo-
tropic system. Therefore, the evolution equation for the structure
parameter must be such that these equilibrium points are reach-
able and linearly stable.
Considering viscometric flows, the flow curve is thus the set of
attractor points of non-equilibrium states on the Cartesian plane
c_  s. In other words, if at some instant of time t0 the point
ðc_ t0 ; st0 Þ on this plane does not belong to the flow curve (Fig. 3),
then it represents a non-equilibrium state of the microstructure,
and hence there is a potential that drives this point along a trajec-
tory that ends at some point on the flow curve.
Therefore, it becomes clear that introducing the flow curve as
input into the thixotropy model defines a priori the correct locus
of atractor points, which constitutes a piece of information that
is crucial to the predictive capability of the model.
It remains to determine which point on the flow curve is the
attractor point for the current state. This issue is not as straight-
forward as it may seem at first glance. For example, in a constant
strain rate experiment, the steady-state situation which corre-
sponds to the current state is defined by the intersection between
the vertical line of the current strain rate and the flow curve. On
the other hand, in a constant stress experiment the steady-state
point corresponding to the current state is defined by the inter-
section between the horizontal line of the current stress and
the flow curve. In these two flows, it may appear that this stea-
dy-state point is the only attractor point throughout the flow,
but it may be not.
As it is explained in the following section, in fact the attractor
point is defined by the characteristics of the evolution equation
for the structure parameter used by the model. Therefore, these
characteristics must bear the correct physics, under penalty of
unrealistic predictions.
6.3. The implicit choice of the attractor point
We now analyze a typical kinetic equation whose form is repre-
sentative of several evolution equations for the structure parame-
ter found in the literature, for the case that k is chosen to vary
between 0 (fully unstructured state) and 1 (fully structured state).
This typical equation is written as
dk 1
¼ ½k1 ð1  kÞ  k2 kgðc_ Þ;
dt teq
where teq, k1 and k2 are non-negative constants and gðc_ Þ is a non-
negative function of the strain rate. Eq. (18) assumes that the build-
up term is proportional to the ‘‘distance’’ (1  k) from the present to
the fully structured state, and that the breakdown term is propor-
tional both to the ‘‘distance’’ (k  0) from the present to the fully
unstructured state and to a function of the strain rate, gðc_ Þ. The
equilibrium (steady-state) value of the structure parameter, keq is
given by
k1
keq ðc_ Þ ¼
k1 þ k2 gðc_ Þ
keq ðc_ Þ is the value of the structure parameter corresponding to the
flow curve at the strain rate c_ .
It is observed that the equilibrium states as given by Eq. (19) are
linearly stable, since, for a small departure from the equilibrium
state Dk, the corresponding derivative of k acquires the sign that
will drive k back to its equilibrium value:
dk k1 þ k2 gðc_ Þ
¼ Dk;
dt t eq
13
For evolution equations like Eq. (18), which possess a break-
down term that is a function of the strain rate, it is seen that the
keq value that is the attractor point for the (non-equilibrium) value
of k at time t depends on the value of the strain rate at the same
time t, say c_ t .
This is better understood with the aid of Fig. 3, where we can
see that a constant strain rate experiment starting at time t = t0
is a vertical trajectory c_ ¼ c_ t0 on the c_  s plane. During the exper-
iment, both the function gðc_ Þ and the equilibrium structure param-
eter keq remain fixed at gðc_ t0 Þ and k1 =½k1 þ k2 gðc_ t0 Þ, respectively.
The point of the flow curve that plays the role of the attractor of
the dynamical system is a fixed point corresponding to the pair
ðc_ t0 ; sðc_ t0 ÞÞ, where the function sðc_ Þ gives the value of s of the
(steady-state) flow curve corresponding to c_ .
A constant shear stress experiment starting at time t = t0 would
lead to a horizontal trajectory s ¼ st0 on the c_  s plane. However,
due to the dependence of the function g on c_ , the equilibrium struc-
ture parameter keq is not constant. Since keq is a function of the cur-
rent value of the strain rate, this quantity varies along the constant
stress trajectory. Therefore, the attractor point on the flow curve
also changes with time. At the current time t, it corresponds to
the point ðc_ t ; sðc_ t ÞÞ on the flow curve, where c_ t0 6 c_ t 6 s1 ðst0 Þ,
and the function s1(s) is the inverse function of sðc_ Þ, i.e. it gives
the value of c_ on the flow curve corresponding to s.
In summary, equations such as Eq. (18) implicitly assume that
the changes of structuring level are dictated by the strain rate.
A totally different response is obtained if instead we employ the
following form of evolution equation for k:
dk 1 c1
¼ ½c1 ð1  kÞ  c2 kf ðsÞ ) keq ðsÞ ¼ ; ð21Þ
dt t eq c 1 þ c 2 f ð sÞ
where teq, c1 and c2 are non-negative constants and f(s) is a non-
negative function of the stress. An equation similar to Eq. (21)
was proposed by De Kee and Fong [9], for a kinetic equation for
the number of structural bonds.
For evolution equations like Eq. (21), in a constant strain rate
experiment (c_ ¼ c_ t0 ) starting at t = t0, the attractor point on the
flow curve changes with time, while in a constant stress experi-
ment (s ¼ st0 ) starting at t = t0, the atractor point is fixed, corre-
sponding to keq ðst0 Þ. Therefore, equations such as Eq. (21)
implicitly assume that the changes of structuring level are dictated
ð18Þ by the stress.
It is thus clear that these two possible kinds of evolution equa-
tion lead to totally different predictions for the dynamic behavior
of the thixotropic system. The recognition of this fact has not re-
ceived the deserved attention and is not an issue commonly dis-
cussed in the literature of thixotropy. A notable exception is
found in Yziquel et al. [7], where three possible causes of structure
destruction are analyzed: the level of strain rate, the first invariant
of the stress, and the level of dissipation. Comparing with experi-
mental results, they conclude that the assumption that dissipation
is the main cause of breakdown was the better choice. However
they did not test the level of stress (represented by the second
ð19Þ
invariant of the stress tensor).
In the next section we discuss the underlying physics of the two
options, namely to assume that breaking of the microstructure is
governed by the stress or by the strain rate.
Before concluding this section, however, we describe how to
use the flow curve as an input of the thixotropic model, irrespec-
tive of the type chosen for the evolution equation or for the stress
equation (Type I or Type II).
Because the structural viscosity is given as a function of k (one
of the assumptions needed in any model), then, if we apply this
ð20Þ
function to the equilibrium state and invert it, then we obtain keq
14 P.R. de Souza Mendes, R.L. Thompson / Journal of Non-Newtonian Fluid Mechanics 187–188 (2012) 8–15
as a function of the equilibrium structural viscosity, which is given
by the flow curve.
The function gðc_ Þ (or the function f(s), depending on the type of
the evolution equation) is readily determined by writing it as a
function of the equilibrium structure parameter keq. Then it can
be eliminated in the evolution equation in favor of keq:
 
k1 1  keq ðc_ Þ dk k1 1  keq ðc_ Þ
gðc_ Þ ¼ ) ¼ ð1  kÞ  k
k2 keq ðc_ Þ dt teq keq ðc_ Þ
or
 
c1 1  keq ðsÞ dk c1 1  keq ðsÞ
f ðsÞ ¼ ) ¼ ð1  kÞ  k
c2 keq ðsÞ dt teq keq ðsÞ
Note that this procedure reduces by one the number of con-
stants of the model (k2 and c2 cancel out), and embeds in the for-
mulation the correct attractor points of the dynamic thixotropic
system by using the flow curve to determine keq.
This procedure, firstly proposed by de Souza Mendes [8], seems
more reasonable than the usual approach, which consists of arbi-
trarily guessing a function gðc_ Þ (or f(s)) and then obtaining a keq
which will be a direct function of this arbitrary guess. The resulting
thixotropy model is usually unable to give acceptable predictions
not even for the flow curve, and, more important, the thixotropic
dynamical system is governed by incorrect driving potentials.
6.4. What breaks the microstructure, is it the strain rate or the stress?
In the previous section we showed that Eqs. (18) and (21) rep-
resent rather different descriptions of the evolution of the thixotro-
pic dynamical system. Therefore, it is important to decide what is
the choice that gives the best description of the physics involved.
In what follows we argue that it seems much more physically
sound to assume that breaking of the microstructure occurs due
to the stress level. This is because the microstructure involves
bonds between structural units, and bonds consist of interparticle
forces. Thus, to break a bond it takes some external force, provided
by the stress level. On the other hand, there is no physical argu-
ment to support the strain rate as the agent that causes bond
breaking. This line of arguments in favor of the stress as the break-
ing agent had already been adumbrated by de Souza Mendes
[8,11], but the evolution equation for k proposed therein is not
quite consistent with this viewpoint. The correct formulation can
be found in de Souza Mendes and Thompson [12].
It is possible to imagine situations in which the stress is zero
but the strain rate is arbitrarily large, and, since there is no stress,
no bond breaking can occur. For example, we can imagine a fully
structured material initially stress-free and at rest, to which at
time t = 0 a constant shear rate c_ is applied. The stress is zero at
t = 0 and increases linearly with time during the elastic regime, un-
til it reaches the yield stress. No breaking of the microstructure is
expected during the elastic regime (by definition of elastic regime
and yield stress).
Since the strain rate is constant in this case, models that assume
that microstructure breakage is due to the strain rate will predict
the highest breaking rate exactly at t = 0 (because k = 1 and gðc_ Þ
is constant), when the stress is zero and hence no breaking what-
soever can occur. On the other hand, models that assume that
microstructure breakage is due to the stress will perform as ex-
pected, because the breakdown term will be zero all the way dur-
ing the elastic regime (since k = keq = 1 and hence there is no
driving potential).
It is also worth examining the performance of models employ-
ing each of the options in the case of a lump of thixotropic elasto-
viscoplastic material, initially at rest and fully structured, on an
inclined plane. Coussot et al. [31] report very interesting experi-
mental results for a related problem.
Before discussing model predictions, it is worth describing the
physical behavior expected. It is clear that, if the inclination is
not large enough to generate stresses above the yield stress, then
the material will remain fully structured and at rest forever, by def-
inition of yield stress. For a large enough inclination, the stress le-
vel in the material is above the yield stress, and hence breakage of
ð22Þ
the microstructure occurs. Therefore, the lump will eventually
start moving and deforming down the plane. If thixotropy is negli-
gible, the flow starts immediately, while, if not, there will be a de-
lay between the moment that the inclination is applied and the
moment that the structuring level becomes low enough to cause
ð23Þ
the viscosity to decrease dramatically, which in turn causes a sud-
den flow to take place—the avalanche effect.
Since the initial strain rate is zero in this case (neglecting elas-
ticity), models that assume that microstructure breakage is due to
the strain rate will predict no breakage1 of the microstructure,
meaning that the lump is predicted to remain at rest and fully struc-
tured forever, regardless of the level of stress! On the other hand, mod-
els that assume that microstructure breakage is due to the stress will
perform as expected. The breakdown term will be zero while in the
elastic regime, and will be an increasing function of the stress in the
case that the stress level is above the yield stress. Moreover, the ava-
lanche effect is nicely predicted, the delay time being determined by
both the stress level and the equilibrium time teq.
It is also important to emphasize that, even when elasticity ef-
fects are not present, it is important to assume that the breakdown
term is a function of the stress rather than the strain rate, as dis-
cussed next.
To illustrate this, it is worth analyzing the Lagrangian motion of
a material particle that occupies a given position in a given instant
of time, in a complex flow of an inelastic thixotropic yield-stress
material. If at this instant of time the material particle is fully
structured (k = 1), then its instantaneous strain rate must be zero
(because zero elasticity is assumed). If the breaking agent is chosen
to be the strain rate, then the breakdown term will always be null.
This means that the microstructure of this material particle is pre-
dicted to never break, regardless the level of stress to which it is ex-
posed. Of course this is unacceptable. On the other hand, it is clear
that the correct prediction is again obtained when the breakdown
term is assumed to be a function of the instantaneous local stress.
Finally it is observed that the two choices for the breaking agent
discussed above become equivalent in the particular case of yield-
stress materials that possess no thixotropy (teq = 0), because k is al-
ways equal to keq in this case. In this connection, it is interesting to
observe that, in this limit of no thixotropy, Type II models reduce to
elasto-viscoplastic models that look like Maxwell or Jeffreys mod-
els, with the structural elastic modulus and structural viscosity
being functions of the equilibrium structure parameter keq. The
resulting models are thus aligned with the standard formulation
used to represent this type of behavior. On the other hand, in the
same limit of teq = 0 (no thixotropy), Type I models reduce to mod-
els that have no resemblance with the usual formulations, and
whose physical interpretation is not quite clear.
7. Final remarks
In this paper the different aspects involved in elasto-
viscoplastic thixotropic models are discussed in detail.
To describe thixotropy, most models rely on the introduction of
a structure parameter, which is a measure of the structuring level
1
Here and in the remainder of this text it is assumed that the function gðc_ Þ
appearing as a factor in the breakdown term is null when c_ ¼ 0, as it is invariably
postulated.
 P.R. de Souza Mendes, R.L. Thompson / Journal of Non-Newtonian Fluid Mechanics 187–188 (2012) 8–15
of the microstructure. This structure parameter is governed by an
evolution equation that associates the rate of change of the struc-
turing level with a competition between the processes of buildup
and breakdown of the microstructure.
In addition to the evolution equation for the structure parame-
ter, all models possess a stress equation and expressions that relate
the structural elastic modulus and the structural viscosity with the
structuring level.
If the stress equation is algebraic and originated from the
Bingham model (Type I models), then an additional equation is
needed to describe the elastic strain ce. For models whose stress
equations are differential and originate from the classic viscoelastic
models (Type II models), no additional equation is needed.
It is argued that the framework of Type II models is more robust,
because
 the underlying physics of Type II models are clearly described
by a mechanical analog, and thus the elastic strain ce—a variable
pertaining to the microscopic description only—does not appear
explicitly in the formulation;
 Type II models can be seen as general models that reduce nicely
to usual formulations for a wide range of special cases of inter-
est, such as inelastic thixotropic viscoplastic materials, and sev-
eral types of non-thixotropic materials like elasto-viscoplastic
materials, and viscoelastic solids and fluids;
 The formulation adopted by Type II models is consistent with
the yield stress concept in its classical sense.
The thixotropy phenomenon is described as a dynamic system
whose equilibrium locus is the flow curve, and the importance of
using the flow curve as an input of the model is explained in detail.
Lastly, it is shown that the breakdown term of the evolution
equation for the structure parameter must be a function of the
instantaneous stress (rather than strain rate), under penalty of an
unphysical description of the thixotropy phenomenon.
Acknowledgments
The authors are indebted to Petrobras S.A., MCTI/CNPq, CAPES,
FAPERJ, and FINEP for the financial support to the Group of Rheol-
ogy at PUC-RIO.
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