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ELSEVIER
J. Non-Newtonian Fluid Mech., 70 (1997) 1-33
Review
Thixotropy
Howard
a review
A. Barnes
Unilever Research Laboratory, Bebington, Merseyside L63 3JW, UK

Received 16 November 1996; receivedin revised form 16 December 1996; accepted 6 January 1997
Abstract
The ensuing mechanical response to stressing or straining a structured liquid results in various viscoelastic
phenomena, either in the linear region where the microstructure responds linearly with respect to the stress and strain
but does not itself change, or in the nonlinear region where the microstructure does change in response to the imposed
stresses and strains, but does so reversibly, The complication of thixotropy arises because this reversible, microstructural change itself takes time to come about due to local spatial rearrangement of the components. This frequently
found time-response of a microstructure that is itself changing with time makes thixotropic, viscoelastic behaviour one
of the greatest challenges facing rheologists today, in terms of its accurate experimental characterisation and its
adequate theoretical description. Here a history of thixotropy is given, together with a description of how it is
understood today in various parts of the scientific community. Then a mechanistic description of thixotropy is
presented, together with a series of applications where thixotropy is important. A list of different examples of
thixotropic systems is then given. Finally the various kinds of theories that have been put forward to describe the
phenomenon mathematically are listed. 1997 Elsevier Science B.V.
Keywords: Microstructure; Stress; Strain; Viscoelastic
1. Introduction
T h e growing use o f c l a y - b a s e d s t r u c t u r a n t s t o g e t h e r with the increasing presence o f flocculated structures in h o m e , p e r s o n a l a n d chemical p r o d u c t s a n d p r e c u r s o r s has led to the
a p p e a r a n c e o f t h i x o t r o p y in a widening range o f situations, quite a p a r t f r o m its presence in
systems long k n o w n to display the p h e n o m e n o n . Difficulties t h e n arise in mixing a n d h a n d l i n g
these materials because t h i x o t r o p i c structures progressively b r e a k d o w n o n shearing a n d slowly
rebuild at rest. T h e time-scales i n v o l v e d can range f r o m m a n y m i n u t e s in the case o f b r e a k d o w n
to m a n y h o u r s in rebuilding.
0377-0257/97/$17.00 1997 Elsevier Science B.V. All rights reserved.
PII S0377-0257(97)00004-9
H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33
Thixotropy has been deliberately built into products to make them usable by non-experts-with the best-known example being thixotropic paints--however, as will be shown here, what is
usually wanted in these cases is extreme shear-thinning. However the way in which this is
brought about usually introduces thixotropy as well, which is then almost always an unwanted
nuisance. However the phenomena still has to be understood, and hence the need for an
up-to-date review.
Major post-war reviews of thixotropy have been produced by Bauer and Collins, 1967 [1],
Mewis, 1979 [2], Cheng, 1982 [3], and Godfrey, 1983 [4]. While the general areas they cover are
also dealt with here, they are well worth consulting for interesting examples of thixotropic
systems not cited here.
2. A history of thixotropy
2.1. Origins
In 1923, Schalek and Szegvari found that aqueous iron oxide "gels have the remarkable
property of becoming completely liquid through gentle shaking alone, to such an extent that the
liquified gel is hardly distinguishable from the original sol. These sols were liquified by shaking,
solidified again after a period of time ... the change of state process could be repeated a number
of times without any visible change in the system" [5]. The term thixotropy was then coined by
Peterfi in 1927 [6], in the first paper that properly described the phenomenon. The work
combines the Greek words thixis (stirring or shaking) and trepo (turning or changing).
Although no mention of the phenomenon appeared in the seminal rheology text of the day
'The Viscosity of Liquids', by Emil Hatschek [7], (especially the chapter on colloidal solutions),
by 1935 Freundlich had published a book called 'Thixotropie' [8] devoted to the subject, having
been the first to introduce it into the title of a paper when he described the flow properties of
aluminium hydroxide gels. Freundlich and co-workers soon found thixotropic effects manifested
by a whole variety of systems including vanadium pentoxide sols, starch pastes, gelatin gels,
pectin gels and many more.
Thixotropy originally therefore referred to the reversible changes from a flowable fluid to a
solid-like elastic gel. Previously these kinds of physical changes had only been known to occur
by changing the temperature, when such gels would melt on heating and then re-solidify on
cooling. It was believed that a new kind of phase change had been found.
2.2. Progress
Early work in this area in the USA is exemplified by a series of three papers by McMillen in
1932 [9], reporting the results of his doctoral investigations into the thixotropy of a large number
of flocculated paints. He showed that the fluidity (the inverse of viscosity) as a function of rest
time decreased in some cases by four orders of magnitude, showing almost a quadratic
dependence on rest time.
Writing in the UK in 1942, Scott-Blair [10] stated that 'the whole subject [of thixotropy] is so
very new'. But then went on to list over 80 papers on the subject (see pp. 61-64). (In the second
edition of this book published in 1949, nearly 120 papers on thixotropy are cited.) Among the
examples of thixotropic materials he gives are clays and soil suspensions, creams, drilling muds,
flour doughs, flour suspensions, fibre greases, jellies, paints, carbon black suspensions and starch
pastes. He also lists a number of papers on so-called thixotrometers, instruments specially
devised to characterise the phenomenon. In this respect he raised some interesting points, among
them whether thixotropy ought to be studied at constant rate of shear or at constant stress? This
is still a most controversial question.
Scott-Blair quotes Hamaker's explanation of thixotropy as being due to the secondary
minimum so that 'particles can form a loose association which is easily destroyed by shaking but
re-establishes itself on standing'. This explanation still stands. With our present knowledge of
microstructural changes, it is probably safe to say that all materials that are shear thinning are
thixotropic, in that they will always take a finite time to bring about the rearrangements needed
in the microstructural elements that result in shear thinning. As Scott-Blair concluded all those
years ago "If this recovery is very rapid, the phenomenon is observed as structural viscosity
[shear thinning]; if slow, it is observed as thixotropy". However even Scott-Blair sometimes
confused thixotropy with shear thinning, as in his example of the importance of thixotropy for
drilling muds that must be runny [sic] when lubricating the drill, but "of a high enough
consistency at rest to avoid settling of suspended matter".
An important point he made concerned a suggestion that certain results of flow in capillary
tubes of suspensions--that we now believe showed migration of particles away from the wall
and thus, have an easier flow in small rather than large tubes--was due to thixotropy. He
refuted this by showing that doubling the tube length halved the flow rate for a given driving
pressure.
Pryce-Jones [11] (the first well-known Welsh rheologist) studied about 250 paints all in a state
of light flocculation, using his own thixotrometer [12]. He noted that "It is a well-established fact
that thixotropy is more pronounced in systems containing non-spherical particles", this is
obviously so because they have to find themselves in the best 3D structure by rotation as well
as movement, and progress from a solid gel to a freely flowing liquid due to complete
microstructural breakdown, see Fig. 1.
Thixotropy is one of the few original technical terms used in pre-war, European rheology
circles that has survived, unlike 'structural viscosity' (Strukturviskositaet, which we now
understand as shear thinning) and 'false body' (now understood as extreme shear thinning with
thixotropy) which have fallen by the wayside ~.
However, as late as 1953, Roscoe [13] still referred to 'false body' as different from thixotropy.
The 'false body' had an apparent yield stress [stress at low shear rate following shearing at a
high shear rate] that recovered quickly, while the thixotropic material takes some times before
relatively fast recovery takes place. Today we understand that they are both manifestations of
thixotropy. False bodies were taking a long time to die.
Jobling and Roberts in 1957 [14] commented that "thixotropy now has an even less distinct
connotation. Electronic methods of measurement have shown that the time-lag required before
Readers with an interest in the historical derivation o f scientific expressions are directed to Scott-Blair [10], p. 52.
All Scott-Blair's b o o k s were written as personal memoirs a n d are very evocative of the m a n himself for those w h o
knew him.
the original structure is regained may be very short indeed and it then becomes difficult to
distinguish between a thixotropic material with a very short recovery time and a material whose
viscosity falls with increasing rate of shear and depends for all practical purposes only on the
instantaneous rate of shear. The latter effect is frequently called 'structural viscosity'". They
went on to say "We endorse Pryce-Jones's plea that in the absence of authoritative definitions,
terms such as ... thixotropy should not be used unless the intended meaning is made clear". In
the Discussion section of this paper, Marcus Reiner notes that 'structural viscosity' and
'thixotropy' are seen as the same thing by some, with structural viscosity seen as a material with
"nearly zero time of recovery".
The full extent of thixotropy was maintained by Bauer and Collins in their 1967 review [1]:
"When a reduction in magnitude of rheological properties of a system, such as elastic modulus,
yield stress, and viscosity, for example, occurs reversibly and isothermally with a distinct time
dependence on application of shear strain, the system is described as thixotropic". They went on
to say that thixotropy was "usually conceived as an unusual property of very special materials,
sol-gel systems such as aqueous iron oxide dispersions, thixotropy in the sense described above
has been found to be exhibited by a great many and a large variety of systems. Along with the
breakdown in structure, other non-rheological features change, such as conductivity and
dielectric constant". Lastly they noted that "The terms used by Freundlich are now seen to be
archaic, viz liquefaction, re-solidification, sol. These had some obvious meaning for the
qualitative changes brought about in low concentration dispersions of highly insoluble oxides of
needle-like crystals such as iron oxide and vanadium pentoxide in low-viscosity aqueous media".
Nowadays thixotropy is sometimes used to include all time effects in a movement to
non-linear behaviour, see for instance Cheng [15], but especially Lapasin and Pricl [16], who
illustrate thixotropic behaviour by the transient response of viscosity and normal force of
S~KING/ Ski,,.
.
Completelystructured- giving ~)~4?>'ft'~,/~--T:~--~.~_2LI

elastic, so,d-,ke response
"-k
Partly structured - giving

viscoelastic response
~'~/4~
~'~-'~'A ~"~//~\~,~,,V~f
." I I ."/.
'-....._~"~-~'~-yt~f ~ / t / ~ - " ; I
'
i/,~'~/-"~/',.-,~-.,~#~~"~~,~ ~i
Completely unstructured
- giving viscous, shear
-thinning response
Fig. 1. Breakdown of a 3D thixotropic structure.
H.A. Barnes / J. NonNewtonian Fluid Mech. 70 (1997) 1-33
polymer solutions. They then noted that the stress overshoot on start-up increases with
increasing rest time. This is an interesting point--build up in polymer solutions is usually
considered to be rapid, and rest times are rarely considered necessary. Weakly cross-linked gels
would give the same thixotropic effect as a flocculated system.
2.3. How is" thixotropy generally understood today7

One of the first definitions of thixotropy was given by Freundlich and Rawitzer [17] who
stated that "By thixotropy is meant the phenomena of concentrated gels ... which solidify to gels
which may again be liquified to sols. The resolidification occurs repeatedly, at constant
temperature with a constant speed". (This would be very far from the kind of definition offered
today.) However, Pryce-Jones [11] soon afterwards stated that the true meaning of thixotropy
was "an increase of viscosity in a state of rest and a decrease of viscosity when submitted to a
constant shearing stress".
It is clear that people using the word thixotropy today fall into two camps: first those who
understand it in the latter (Pryce-Jones) sense as the time response of the microstructure brought
about by shearing or resting, respectively, and the rheological effects arising therefrom. In these
circles it is often used in a very narrow sense of viscosity changes only, with no reference to the
reversible transition from gel-like to fluid-like behaviour.
Secondly there are those--often in industrial circles--who understand thixotropy in its
original Freundlich and Rawitzer sense, as stated above, of conferring gel-like properties to a
liquid which disappear on shaking but reappear on standing. This particular property adds
considerable advantage to the practical use of materials such as paints, adhesives and coatings.
Unless this different use is borne in mind, severe misunderstand will arise on reading the general
literature. The former group would understand the use of thixotropy by the latter group as
conferring extreme shear thinning to a liquid by, for instance, the addition of so-called
thixopropes or by inducing flocculation. On the other hand the latter group only see the
temporal properties of thixotropy as an irritation, because the desired reversible gelled state they
want takes some time to disappear on shearing or reappear on standing. It is not surprising
therefore that thixotropy has, on occasions, been confused with shear thinning.
There are various definitions of thixotropy offered in the current general scientific literature,
e.g., scientific dictionaries and encyclopedias, that reflect these two points of view. Some are
misleading, with even the best being incomplete. The following are a selection that illustrate the
situation:
Oxford Encyclopedic Dictionary of Physics, [18]--"Thixotropy: Certain materials behave as
solids under very small applied stresses but under greater stresses become liquids. When the
stresses are removed the material settles back into its original consistency. This property is
particularly associated with certain colloids which form gels when left to stand but which
become sols when stirred or shaken, due to a redistribution of the solid phase."
Chambers Dictionary of Science and Technology [19]--"Rheological property of fluids and
plastic solids characterised by a high viscosity at low stress, but a decreased viscosity when an
increased stress is applied. A useful property of paints, because it makes for a thick film which
is nevertheless easily worked."
McGraw-Hill Dictionary of Scientific and Technical Terms [20]--"Property of certain gels

which liquify when subjected to vibratory forces, such as ultrasonic waves or even shaking,
and then solidify again when left standing. Thixotropic clay: a clay which weakens when
disturbed and increases in strength upon standing."
Van Nostrand's Scientific Encyclopedia [21]--"A thixotropic fluid is a fluid whose viscosity
is a function not only of the shearing stress, but also of the previous history of motion within
the fluid. The viscosity usually decreases with the length of time the fluid has been in motion.
Such systems commonly are concentrated solutions of substances of high molecular weight, or
colloidal suspensions."
Oxford Concise Science Dictionary [22]--"More common, however, is the opposite effect in
which the viscosity depends not only on the viscosity gradient but also on the time for which
it has been applied. These liquids are said to exhibit thixotropy. The faster a thixotropic liquid
moves the less viscous it becomes. This property is used in nondrip paints (which are more
viscous on the brush than on the wall) and lubricating oils (which become thinner when the
parts they are lubricating start to move)."
Chambers 20th Century Dictionary [23]--"Thixotropy: the property of gels of showing a
temporary reduction in viscosity when shaken or stirred."
Definitions given in more specialised dictionaries emphasise the time aspect of thixotropy:
Polymer Technology Dictionary [24]--"Thixotropy. A term used in rheology which means
that the viscosity of a material decreases significantly with the time of shearing and then,
increases significantly when the force inducing the flow is removed."
Polymer Science Dictionary [25]--"Time-dependent fluid behaviour in which the apparent
viscosity decreases with the time of shearing and in which the viscosity recovers to, or close
to, its original value when shearing ceases. The recovery may take place over a considerable
time. This may sometimes occur with polymer systems, when molecular disentanglement
increases with time of shearing."
The definition of thixotropy in the rheological literature has changed over the years. The
(American) Society of Rheology was quoted by Reiner and Scott-Blair in 1949 [26] as having
defined thixotropy as "that property of a body by virtue of which the ratio of shear stress to rate
of deformation [viscosity] is temporarily reduced by previous deformation". Some time later
thixotropy was defined as "a comparatively slow recovery, on standing, of the consistency lost
through shearing". However, thixotropy has recently been defined by Barnes, Hutton and
Walters [27] (following the 1975 British Standards Institution definition) as the "decrease [in
time] of ... viscosity under constant shear stress or shear rate, followed by a gradual recovery
when the stress or shear rate is removed". (As we shall see, this is not a comprehensive
description of the p h e n o m e n o n - - a better description would cover the temporal rheological
response of a microstructure to changes in imposed stress or strain rate.)
It is obvious then that while most rheologists take a general view of thixotropy which covers
all time effects resulting from microstructure changes, in the popular image, the older idea of a
gel-sol transition on shearing-resting is still often held. Strictly speaking, what is usually meant
by thixotropy in that case would now be termed 'extremely shear thinning', to give near
solid-like properties at rest but flow under stress, as for instance in thixo-forming using
semi-molten metals or the addition of so-called thixotropes to paints.
A better and extended definition of thixotropy is clearly needed, and it should contain the idea
of both considerable shear thinning (i.e., gel-fluid transition) and also time changes over and
above those encountered when in its structured state the thixotropic material might be
viscoelastic with its attendant time effects.
3. Description of the phenomenon

3. I. General considerations
All liquids with microstructure can show thixotropy, because thixotropy only reflects the finite
time taken to move from any one state of microstructure to another and back again, whether
from different states of flow or to or from rest. The driving force for microstructural change in
flow is the result of the competition between break-down due to flow stresses, build-up due to
in-flow collisions and Brownian motion. Brownian motion is the random thermal agitation of
atoms and molecules that results in elements of the microstructure being constantly bombarded,
which causes them to move to a favourable position where they can--given the necessary
attractive force--attach themselves to other parts of the microstructure. Very occasionally
situations arise where existing weakly attached microstructural elements--brought together by
collision during shear--are slowly torn apart by the constant action of the random Brownian
motion. In that case, the opposite to thixotropy is seen, i.e., antithixotropy, where flow
structures and rest destructures the material.
The term microstructure, as used here, while usually associated in thixotropic systems with
flocculated particles, can also mean alignment of fibres; favourable spatial distribution of
particles or drops, or entanglement density or molecular associations in polymer solutions. All
these determine the level of viscosity and elasticity, and they all take time to change from one
state to another under the action of shear and/or Brownian forces. In these cases, the maximum
microstructure is seen when alignment and spatial distribution are random (in three dimensions)
and entanglement density is at a maximum. Both these conditions result in the greatest viscous
(and usually elastic) response. On the other hand, minimum microstructure is when there is
maximum alignment with the flow of fibres; the drop or particle spatial distribution is
asymmetrical in the flow direction, or there are a minimum number of entanglements or
associations--all these leading to minimum viscous and elastic response.
When the timescales displayed in these changes become long compared with either the
response time of a viscometer (or rheometer), or the flow-time in a particular flow geometry, we
can speak sensibly about thixotropy. These timescales often range from seconds to hours, with
rebuilding usually taking much longer than breakdown.
H.A. Barnes/J.
N o n - N e w t o n i a n F l u i d M e c h . 70 (1997) 1 - 3 3
+,a
.......................e q u i l i b r i u m .............................................
shearing time
Fig. 2. Shearing a thixotropic liquid after short and long rest times.
3.2. Typical behaviour

If we place a thixotropic material into a viscometer (see Fig. 2) and apply a constant shear
rate, the measured viscosity will decrease with time, but it will eventually steady out to a
constant value. If we then switch off the shear and allow the material to rest for a long time
(without drying or any other artifacts such as sedimentation or separation occurring), and
switch the shear on again, the measured viscosity will be initially higher, but it will then again
decrease and end up at the same value as that which was seen after the original long-term
shearing. However, the level for the original value will not necessarily be the same, because that
will depend on how carefully or vigorously the material was initially loaded into the viscometer
and how long it was left to rest before shearing.
If on the other hand a third experiment is performed where the material is allowed to come
to equilibrium and then allowed to rest for the same time as before, the results will be identical.
If now, after equilibrium is achieved, the shear rate is instantaneously decreased to a lower
value, the measured shear stress drops instantly, but thereafter it will slowly increase towards a
new equilibrium.
(If instead of applying a given shear rate we applied a particular shear stress, then the inverse
applies--the shear rate would increase as the structure breaks down and the change to another
(lower) shear stress will result in a sudden decrease in shear rate followed by a further drop, see
Fig. 3.)
If we now enquire what is happening on a microscale, we can imagine the picture presented
in Fig. 4, where the viscosity/shear-rate behaviour of a typical thixotropic material (which for
the sake of argument could be a flocculated suspension) is presented. We start from point a
where the microstructure at rest is a series of large flocs. Then if the applied shear rate is
increased progressively and sufficient time allowed, the floc size decreases until at a high enough
shear rate, the floc has disintegrated completely into its constituent primary particles.
We now imagine another experiment where the shear rate is increased step-wise from a to end
up at point b. Instantaneously, the floc size will be that appropriate to the shear stress conditions
at point a, but as it experiences the higher shear rate at position a', it begins to erode, until it
reaches an equilibrium size appropriate to the higher rate. This process can take some time. If
now the opposite happens--the shear rate is instantaneously decreased--the individual particles
H.A. Barnes//J. Non-Newtonian Fluid Mech. 70 (1997) 1-33
STEP EXPERIMENTS
J~
. . . . . . . . . . . .
-4_ . . . . . . .
~ ~ . ~
...........
......
Time
,T
i
Time
values
equilibrium
-~
>
>
Time
>
Time
Fig. 3. Two kinds of step experiment.

(which gave the low viscosity) begin to collide and flocculate until the size of the floc so-formed
is appropriate to the new, lower shear rate. This process also takes time, but the build-up
proceeds at a different rate than does breakdown.
Any concentrated suspension of particles is shear thinning, thus when we consider flocs, they
too will show the phenomena as illustrated in Fig. 4. If we imagine that the particles in a floc
are permanently glued together and thus, the floc size is fixed, the flow curve of such a
suspension of fixed-size flocs would follow the lines shown in the figure according to the floc
size. If the floc size is now decreased (and the overall concentration maintained) but again the
floc size remains unchanged when sheared, the flow curve will be lower and (for a given
concentration) the degree of shear thinning decreases.
~a
,t=
shear rate (log scale)

Fig. 4. Microstructure and flow curves of a flocculated suspension.
10
H.A. Barnes /J. Non-Newtonian Fluid Mech. 70 (1997) 1-33
However because we are interested in systems flocculated in a secondary minimum, the floc
size is not constant but decreases with increasing shear rate (or shear stress). Because the
viscosity decreases with floc size (see above), we now have a double shear-thinning effect. This
means that flocculated systems are very shear thinning, see the equilibrium curve in Fig. 4. This
extreme shear-thinning also results in such flocculated, thixotropic systems appearing to have a
yield stress, since the stress only decreases very slowly as the shear rate is decreased.
The true steady-state behaviour of a thixotropic liquid is seen both after an infinite shearing
time at any shear rate or shear stress of interest or infinite rest time. Of course, as all these
equilibrium states are approached asymptotically, one comes close to this state after a reasonable rather than an infinite time, but even then, breakdown times of hours and rebuilding times
of days might be necessary to fully describe a very thixotropic system.
In a flocculated system, breakdown is towards an equilibrium situation that is governed by a
balance of hydrodynamic shear stresses pulling structures apart by erosion, and a combination
of Brownian and shear forces building the structure up by collision and accretion of particles
which agglomerate into flocs. The forces holding the structure together are colloidal in nature,
acting over short distances ( ~ 10 nm) within the composite particle. At rest, only the Brownian
rebuilding forces are present, and these are quite small compared to the shearing forces, being
of order 1 kT. This means that the rebuilding time can be very long, since this small, random
force takes a long time to rearrange large particles that as flocs are getting larger and larger as
they move into a most favourable structure, which is then manifested as a higher and higher
viscosity.
The typical response to a step-wise change from one steady state condition to another is, in
terms of the viscosity, often characterised by the so-called stretched exponential model:
F/ = Y]e,oQ -~- (g/e,~
-- r/~,o)(1
--
e-(t/~)~),
(1)
where r/e,0 is the viscosity at the commencement of shearing, ~/e.~ the viscosity after shearing for
an infinite time, z is a time constant and r is a dimensionless constant (which in the simplest case
is unity). This equation can cope with build-up and break-down in step-up or step-down tests,
with the values of ~ and r depending on both the level and the direction, i.e., going from 10 to
1 s - 1 will not have the same value of f found in going from 1 to 10 s - 1. The values of r also
vary with the conditions of the test, as well as the particular system being tested, and they
decrease linearly with the log of the shear rate, typically from 0.7-0.9 at l0 -2 s-1 to 0.3-0.4
at 1 s - 1 in Mewis' experiments [28]. He also showed that for a typical flocculated system (fumed
silica in paraffin oil), z is a decreasing function of r/e.O ~/~/oont, where qcont is the viscosity of the
continuous phase, which when taken into account, properly describes the effect of temperature.
(He also reports optical, dielectric and conductivity results on these systems).
Heymann et al. [29] investigated the build-up after shearing of the yield stress of five
newsprint inks, with the formulation containing carbon black. A period of pre-shearing was
carried out at 1500 Pa, and then the flow curves were measured as a function of time. For those
inks, judged to have a yield stress ~y, an equation similar to Eq. (1) was used to describe the
rebuilding:
rat)
Oyo + [try -- or](1 -- e-~t/~))
(2)
11
For these materials so described, the values of v were found to be well over 100 s. For this
reason, it was judged that the recovery behaviour had no relevance to the printing process,
because these process times are of the order of a few seconds at most.
Not only can shear break down or build up flocs, but it can also change their internal
morphology. For instance, the work of Mills et al. [30] showed that shearing freshly prepared
flocculated suspensions can densify individual floes, causing reorganisation within the flocs. This
shows how important it is to 'condition' such systems before shearing them in experiments to
elucidate their thixotropic behaviour. They found that following prolonged shearing, loosepacked flocs became tightly packed and more monodispersed. This can be interpreted as a
permanent loss of structure--rheomalaxis or rheo-destruction.
The experiments of Wolthers et al. [31] show us how important thixotropy can be in a typical
flocculated systems. They examined the behaviour of a depletion-flocculated polymer latex
suspension and showed that the shear stress dropped significantly with time, and was still
decreasing after 1 h. The values of the initial and final viscosities they found were at least an
order of magnitude different. They also found that the unsheared samples were more open flocs
while shearing made to fresh flocs more dense.
3.3. Antithixotropy
As we have already seen, given the right kind of attraction between particles, shearing can
promote temporary aggregation rather than breakdown, due to the collision of these attractive
particles--this results in anti-thixotropy. Doraiswamy et al. [32] have shown that the average
agglomerate size of a suspension in shear was given by
r
-- = exp[(8~b~Et)/3Tc],
(3)
F0
where E was the probability that a collision of particles would result in agglomeration, and r and
r0 were the radius of the sheared and unsheared flocs, respectively. They then described an
experiment where a 12% phase volume suspension of inorganic pigment in a low molecular
weight polymeric fluid grows from 3.4 to 88.1 jam after flowing through a 50 m long tube of
diameter 0.038 m. This meant that the value of E was as low as 0.006. They pointed out that this
value will tend to zero above a critical stress when the agglomerates begin to disintegrate. In
separate experiments on a 4 gm glass beads in corn syrup suspension in a cone-and-plate
viscometer, they showed that the agglomerate size tended to a steady value after shearing for
more than about 2 h. Chang and Smith [33] showed that this kind of behaviour is seen in certain
nuclear waste simulate slurries, especially if silica (SiO4) is present.
Antithixotropy can also arise because certain floes can become looser and more open under
the action of shear and thus the viscosity increases. One good example of this negative (or anti-)
thixotropy is ferric-oxide suspensions in mineral oil, see [34]. Suspensions of acicular, fine
maghemite are known to show a strong tendency to flocculate due to the magnetic properties of
the particles. Like other such suspensions, there is a range of flow conditions under which
shear-enhanced collisions make structure rather than break it. In this case the onset of
antithixotropy is around 50 s 1. Below that range the suspensions are thixotropic in the normal
way, while above this critical value, strong anti-thixotropy sets in. They conclude that the shear
loosens the ftocs, which then have a higher effective phase volume.
12
viscoelastic response
inelastic, viscous response
~ equ~
shearing time, t
shearing time, t
Fig. 5. Different kinds of thixotropic behaviour on start up of shear after various degrees of rest (neglecting
instrument inertia).
4. Viscoelasticityandthixotropy
Viscoelastic systems sheared in their linear region show time-dependency because the microstructure takes time to respond to the flow/stress. At short times (high frequencies) the
structures cannot respond quickly, and we see an elastic response, while given time (low
frequencies), the system can adjust itself continuously, i.e., it can flow, showing viscous effects.
Thus, when observed over all time (and frequency) scales, the system is viscoelastic.
For non-linear viscoelastic--or simply inelastic but shear-thinning systems--not only does
the microstructure take time to respond to the flow, but it is also changed by the flow and this
change will itself take time. This is the essential difference between linear viscoelasticity and
thixotropy--that while both are time effects, the former is in the linear region, where the
structure responds but remains unchanged and the latter takes place in the non-linear region
where the structure is broken down by deformation as well as responding to it.
Shear thinning can occur for many reasons, e.g.,:
alignment of rod-like particles in the flow direction;
loss of junctions in polymer solutions;
rearrangement of microstructure in suspension and emulsion flow and
breakdown of flocs.
Since changes in any of these states take some time to come about (either from rest or from
some other configuration), thixotropy is always (in principle) to be expected from any shearthinning mechanism. However thixotropy becomes significant when the time-scale over which it
is seen becomes significantly longer than the response times of instruments used to measure
rheology or longer than some flow time in a process, e.g., the average time a liquid takes to flow
through a pipe. Thixotropic timescales can be longer than viscoelastic timescales and are
practically important when these timescales become minutes and longer for breakdown. This
will inevitably mean many more minutes or even hours for recovery of the structure. Given the
nature of most microstructural features which produce thixotropic effects (see above), it is
obvious that at conditions near the fully structured rest state, viscoelastic effects will also be
seen. The typical response to a startup experiment from a rested state shows this, see Fig. 5.
Only a few theories have sought to account for this effect, which shows concurrently a
breakdown/rebuilding of both viscous and elastic responses.
13
The picture presented becomes even more complicated when we consider the linear viscoelastic response of a rebuilding structure, where the typical storage and loss m o d u l i - - G ' and
G"--curves evolve with time. This can be used as a measure of the rebuilding mode since the
test is conducted at low-enough stresses/deformations that the evolving structure is unaffected
by the deformation. The growth of G' particularly is very sensitive to structure rebuilding. Barut
et al. [35] studied an acrylic polymer solution in a mixture of solvents, with TiO2 or a mixture
of TiO2 and alumino-silicate particles. These were pre-sheared in a controlled-stress rheometer
at 200 Pa for 2 min and after this ceased, the linear oscillatory properties were monitored for
10 min at strains less than 0.1 over a frequency range 0.03-62.8 rad s 1. The form of the
rebuilding curve of the storage modulus was of a stretched exponential form:
G' = G k - ( G " -
G;)exp( - ktP).
(4)
Williams and Ren [36] used the Virtual Gap Rheometer operating over the range 250-800 Hz
to examine the rebuilding of 0.045 g ml-1 aqueous Laponite RD dispersions (synthetic
hectorite-type clay, circular discs ,-- 300 x 10 A), again measured by G' but now derived from
the phase velocity. At these high frequencies, G' is a particularly sensitive measure of structure
as the solid-like response of the clay. They showed that restructuring was significant over the
first 10 min or so, but was still going on after 20 min. Viewed on a log scale there is a rise from
an initial value at small times and a fast build up through a power-law region, eventually (as it
must) flattening out at times greater than 20 min.
Bouda and Mikegovfi [37] simultaneously monitored the AC conductivity and the storage
modulus G' to establish the buildup of a carbon black network in a polyethylene melt. After an
initiation period where the conductivity was constant, it then increased rapidly. The time a 7.4
weight % sample took to show the rapid increase was nearly 200 rain. Similar behaviour was
also observed for G'. They explained the observations as resulting from the setting up of a
continuous network, and using percolation theory showed that the observed behaviour was
explainable on the basis of diffusion-limited aggregation of small clusters of primary carbonblack particles under the action of Brownian motion. As the flocs collide and stick together they
eventually form an interconnecting network as the percolation threshold is reached, at which
point both the electrical conductivity and the storage modulus G' rose rapidly, see also [38].
On the other hand, Greener and Connelly [39] point out how easy it is to misinterpret
thixotropic loops, particularly if there is viscoelasticity present in the sample being tested. They
compare the supposed thixotropic behaviour of an aqueous polyacrylamide solution with the
predicted behaviour of the Wagner model and show that all the effects are accounted for by the
non-linear viscoelastic behaviour, and not by true thixotropy!
5. Typical thixotropic experiments

5.1. Thixotropic /hysteresis loops
One of the favourite ways of measuring thixotropy is to perform a loop test; that is to say,
to linearly increase the shear rate (or sometimes shear stress) from zero to a maximum value,
and then to return at the same rate to zero. This test could then be repeated again and again,
14
H.A. Barnes / J . Non-Newtonian Fluid Mech. 70 (1997) 1-33
until eventually, a constant loop behaviour is seen, see Fig. 6. The area between the up and
down curve is automatically measured in some computer-based rheometers as a measure of
thixotropy.
This kind of test is to be depreciated, for although useful as a quick, qualitative procedure it
has a number of bad points. First, the loop test is often carried out too quickly, and inertia
effects due to the measuring head are introduced but not always recognised. (However, inertial
effects can now be accounted for by some rheometer software packages.) Secondly, a test where
both shear rate and time are changed simultaneously, on a material where the response is itself
a function of both shear rate and t i m e - - a s thixotropy obviously i s - - i s bad experimentation,
because the response cannot then be resolved into the separate effects arising from both
variables. However the problem in interpreting the loop is even more difficult when we realise
that the first part of the behaviour on start-up is essentially elastic. As the strain becomes large,
this moves to non-linear elastic response. If the behaviour were just linear elasticity, then the
strain in a simple loop test increases parabolically, and the curve is concave to start with, but
soon turns over. At the same time the viscous behaviour can become apparent in the first
tendency to flatten out. The viscous behaviour then itself becomes nonlinear as the structure
begins to break down at large strains. As the strain rate increases further, the liquid would like
to shear-thin, but this takes time since the structure cannot adjust itself fast enough to respond
to the increasing shear rate. When the time is long enough and the structure has broken down,
the down curve will be under the up curve. Rebuilding will then begin to take place slowly. Even
with an apparatus that responds perfectly to the stress and strain, interpreting the data to obtain
the parameters corresponding to a model is very difficult if not impossible.
A simpler and more sensible test for a thixotropic liquid is performing and deriving results
from step-wise experiments where the shear rate or stress is changed from one constant value to
another with a carefully controlled prehistory. Even so, it is impossible to eliminate an elastic
response and instrument inertia.
5.2. Start-up experiments

Any experiment that starts from rest is another kind of thixotropic test. The typical behaviour
of strain- or stress-controlled experiments is shown in Fig. 7. Most, if not all, thixotropic
. . . . . . . . . .
second loop
n'th loop
shear rate, 1/s

Fig. 6. A typical thixotropic-loop test.
15
time of shearing
Fig. 7. Various flow regimes after start up.
materials that have been at rest for some time show viscoelastic behaviour, so the immediate
response in such tests is elastic, then depending on the conditions, a thixotropic response will be
seen either as an overshoot in the stress in strain-controlled experiments or an increase in the
slope of the strain-time curve in creep tests. This sometimes happens after a critical strain has
been achieved. This initial elastic response giving way to a thixotropic viscous response makes
the behaviour quite complicated.
5.3. Artifacts involved in measuring thixotropy

The greatest difficulty in understanding and modelling thixotropic materials is knowing the
effect of t h e - - o f t e n u n k n o w n - - d e f o r m a t i o n prehistory on the liquid of interest. This is
particularly true in situations where a thixotropic liquid is subject to mixing and pumping, or
even the seemingly simple task of filling a viscometer or rheometer. In both cases it would be
interesting to be able to predict the subsequent flow even if only the initial response was known,
say the initial torque on a viscometer operating at a certain shear rate, or the torque on a mixing
vessel prior to the liquid being pumped out.
A number of methods have been devised to establish a consistent initial condition: fixed rest
time after sample loading; pre-shear at a prescribed shear rate for a prescribed time followed by
a set rest period; pre-shearing to equilibrium at a low shear rate followed by testing at a higher
shear rate, etc. These eliminate the problem in characterisation, but they can never completely
eliminate the problem in practise, since the effects of prehistory on a previously untested sample
is always unknown.
The mechanical inertia of the rotating members in viscometers and rheometers means that in
experiments where the shear rate or stress is changed quickly or instantaneously, the instrument
response is delayed, and this is often mistaken for thixotropy, and, even if thixotropy is present,
it can complicate its measurement. Sometimes the presence of a low compliance spring
complicates the measurement because the output of the experiment relates to the spring winding
up.
For thixotropic materials, as we have seen, a typical source of the phenomenon is breakdown
of flocs. However the appearance of apparent slip at the wall, e.g., depletion, can also arise from
flocs because they are large, see Barnes [41]. This is a case where observing the pressure gradient
16
alone will not differentiate or account for both effects. A detailed investigation of the internal
flow profile will alone show what is happening. As well as pipe flows, there are many apparently
simple flows where the shear rate or shear stress is not constant spatially, for instance wide-gap
concentric cylinders and parallel plates. These geometries are often used in the rheological
characterisation of thixotropic liquids, and unwittingly many workers are unaware of the
complications.
6. Engineering consequences of thixotropy

6.1. Flow in mixers
Edwards et al. [40] found that the behaviour of a range of thixotropic materials in a series of
mixers was quite easy to characterise if one assumed that the mixer behaved in the same way as
a viscometer running at the same shear rate as the average shear rate in the mixer. They used
an average shear rate for the flow in a cylindrical vessel with anchor, helical ribbon and helical
screw impellers, given by the impeller rotational speed N (rev s - l) times a constant depending
on the impeller geometry, k, where values of k ranged from about 12 for the helical screws,
around 20 for the anchor to 30 for the helical ribbon. They compared the torque produced in
the mixer with the signal from a viscometer running at the same shear rate, both of which could
halve over the course of the experiment. For salad cream, tomato ketchup, yoghurt, paint and
3 and 4% aqueous Laponite dispersions, they found that the average viscosity measured as a
function of time in the mixer at a given impeller speed compared well with that from a
viscometer running at the same shear rate. For the salad cream, tomato ketchup, yoghurt and
paint, the viscosities agreed to within 10%. The predicted values for 3 and 4% Laponite agreed
reasonably well for the anchor and helical ribbon, but were between 20 and 40% too low for the
helical screws. This latter fact was probably due to the very non-Newtonian and thixotropic
nature of the Laponite dispersions.
6.2. Flow in pipes
When a thixotropic liquid enters a long pipe from a large vessel where it has been allowed to
rest, the development of the velocity and pressure fields in the pipe is very complicated. The
large pressure involved in the start-up of flow of a thixotropic liquid can cause significant
problems in terms of the necessary pump performance. Often cavitation can be caused because,
although a pump could cope with sheared material, it might be unable to initiate flow of
material that has been at rest for some time. Cavitation in the liquid within the pump can then
ensue.
Once flow has started, the liquid near the pipe wall is subjected to the highest shear rate but
the lowest velocity, hence it is subjected to the shear for longer than the fluid flowing at the
middle of the pipe. This results in a very fast and prolonged breakdown near the wall, giving a
low viscosity layer that effectively lubricates the inner, more-viscous layers. If the pipe is long
enough, the flow profile will evolve such that eventually the steady state profile is established.
However, for short pipes, characterising the flow can be quite complicated, with a non-linear
17
pressure profile down the pipe being a distinct possibility. Distinguishing thixotropy from a
developing slip layer caused by particle depletion can be very difficult (see Barnes [41]).
Simple approaches have been made to analyze this problem mathematically, see Godfrey's
summary [4], but the ones worth mentioning are due to Kemblowski and Petera [42] and Cheng
and co-workers [43]. The kinds of important situations analyzed include start-up of fully
structured thixotropic fluids and then steady-state flow, in both cases with either a constant flow
rate or a given pressure drop. The analysis was complex and required extensive numerical
computation.
7. Examples of systems and studies from the literature

There is a very large number of systems that have been found to be thixotropic; previous
reviews have listed many examples (see Bauer and Collins [1], Mewis [2], Cheng [3], and Godfrey
[4]). Here a set of largely new examples are given, with special emphasis on hitherto unreported
eastern European and oriental studies. In order to save space, a large number of examples are
presented in tabular form in Tables 1 and 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8
Table 9 Table 10, grouped appropriately, with each paper summarised in one phase. Reference
can be made to them at the reader's convenience. Then follows a more detailed discussion of
some recent examples.
7.1. Thixotropic paints, inks and coatings (see Table 1)
When coatings are applied to vertical or inclined surfaces, the time taken for rebuilding to
occur can cause the material to drain. This is obviously undesirable. The thixotropic breakdown
of paints is important when such paints are being put onto the brush or brushed out. The
desirable properties of non-drip might appear quite quickly, but the paint has to be worked to
make it thin enough to apply evenly.
7.2. Thixotropic detergent systems (see Table 2)
Thixotropy in commercial detergent liquids can give rise to problems when they have to be
poured from containers or poured into machines. Then dispersion can be a problem. If
rebuilding is very slow, physical instability can result due to sedimentation or creaming.
7.3. Thixotropic clay suspensions (see Table 3)
Clays are probably the best known examples of thixotropy, because of the extreme changes
brought about under shear. A clay suspension can be shaken in a bottle, and the sound
generated is almost water-like, but on standing the clay can become completely gelled and
manifests a ringing sound if tapped in a glass container. Clays such as the natural Bentonites
and the manufactured and modified Laponites, because of the extensive nature of the very thin
sheets from which they are made up, give a very good thickening effect at relatively low
concentrations, without giving unwanted viscoelastic effects found with some kinds of polymeric
18
Table 1
Paints, inks and coatings
Author(s)
Ref.
Details
Overdiep
Kuwano et al.
Iizuka and Naganuma
Cornelius
Galli
Kutik
Kerle
Pila
Papo and Sturzi
Parmentier
Dubyaga et al.
Alessandrini
Walton
Crawford
Staus and Edser
Berry
Iizuka and Naganuma
Kobs and Voigt
Tsuritani
Toussaint
[44]
[45]
[46]
Effect of thixotropy on film formation

Thixotropy in automobile paints
Review of thixotropes for paints
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
Thixotropy in urethane modified alkyd resins

Fumed and precipitated silica, and clays as thixotropes for plastic coatings
Amorphous silica gel as thixotropes
Thixotropy in polyester-based thixotropic resins
Thixotropes for vinyl resin thick layer systems
Bentone as a thixotrope for oxidised bitumen protective coatings
Hydrogenated castor oil as thixotrope for wood treatment coating
Effect of thixotropy on film properties of polyether polyurethanes
Montmorillonite thixoptrope in oxidised bitumen paint
Production of thixotropic paints
Review of advantages of thixotropy for all coatings
Thixotropic vinyl-based polymer household emulsion paint
Thixotropic alkyd-resin and polyamide-based household paints
Thixotropes for high-solids coatings
[61]
[62]
[63]
Effect of thixotropy on thick film screen printing

Thixotropy of printing suspension and paste inks
Thixotropy in organic coatings
thickeners. H o w e v e r because o f the size o f the clay plates the rate o f structuring is very slow a n d
also the difference between the fully f o r m e d structure at rest a n d the flowing dispersion is very
large.
7.4. Thixotropic oils and lubricants (see Table 4)

Greases are thixotropic because o f the flocculation o f the dispersed material suspended in the
oil phase. This is very i m p o r t a n t in lubricating situations where the grease has to break d o w n
on shearing so t h a t no u n w a n t e d extra d r a g is experienced in bearings.
Table 2
Detergent systems
Author(s)
Ref.
Wolff
[64]
Rounds
[65]
Moreno et al. [66]
Moreno et al. [67]
Details
Thixotropy in micellar surfactant solutions containing aromatic solubilisers
Thixotropic in rod-like micellar surfactant solutions
Thixotropy in systems containing anionic surfactant, ethoxylated alcohol, and sodium or
triethanol-ammonium sulfate
Effect of ethanol, urea, or sodium silicate on thixotropic properties of commercial heavy
duty liquid detergents
19
Table 3
Clay suspensions
Author(s)
Ref.
Details
Aripov
Legrand and
Costa
Haret and Zarea
Shevchuk and
Shishkevich
Orazmuradov et
al.
Ryabchenko and
Agabal'yants
Schulz
Egashira
Rosenqvist
Nakaishi and Yasutomi
Bendukidze et al.
Txoperena
[68]
[69]
Thixotropy of montmorillonite dispersions

Effect of shearing on thixotropic bentonite muds
[70]
[71]
Effect of vibrations, electrolytes and temperature on thixotropy of clays

Effect of oil-water emulsions on thixotropy of montmorillonite-based muds
[72]
Effect of electrolyte and various colloids on thixotropy of bentonite clay suspensions
[73]
Orientation-thixotropic effect in aqueous dispersions of montmorillonite clays
[74]
[75]
[76]
[77]
Review of modified Bentonite (organoclay) organophilic thixotropes for coatings

Effect of colloid chemistry on thixotropy of clays
Thixotropy in quick clay
Effect of time scale of measurement on flow of clay suspensions
[78]
[79]
Effect of Bentonite on storage properties of chlorinated rubber enamels

Thixotropy in coatings for wood paints and varnishes
7.5. Thixotropic coal suspensions (see Table 5)

Coal-oil and coal-water
with start up of pumps
duties required for flow of
rested suspension. This can
high.
suspensions show considerable thixotropy, and problems

after stopping the flow can cause problems. The p u m p
sheared suspensions are very different from start up of a
result in pump failure, since start up torques can be very
Table 4
Oils and lubricants
Author(s)
Ref.
Details
Wislicki
Czarny
Szilas
[80]
[81]
[82]
Thixotropic properties ester-based synthetic lubricating oils

Thixotropy in lithium and calcium-based greases
Thixotropy in crude oils flowing in pipelines
20
Table 5
Coal suspensions
Author(s)
Ref.
Details
Usui
De Jong
Chakraborty
Sabadell et al.
[83]
[84]
[85]
[86]
Thixotropy
Thixotropy
Thixotropic
Thixotropy
and physical stability of coal slurries

of coal-water mixtures
coal-water suspensions
of coal-oil suspensions
Table 6
Metal slushes
Author(s)
Ref.
Details
Erz
[87]
[88]
[89]
[90]
Thixocasting--a casting process for near-net-shape manufacture aluminium alloys

Thixotropy of two-phase metallic slurries
Review of thixo-casting
Thixotropic of semi-solid aluminum-6% silicon carbide alloy reinforced with silicon carbide particles
Vives et al.
Flemings et al.
Mada and
Ajersch
7.6. Thixotropic metal slushes (see Table 6)

If metals are sheared just below their melting point, they take on the appearance of a
shear-thinning liquid. However, they have been described as thixotropic. While they might show
some thixotropy, the title is probably a misnomer because shear thinning is perhaps even more
important than thixotropy. In fact, as stated above, thixotropy is probably a nuisance, because
what is needed is a fast-responding, very shear-thinning, liquid-like material for casting.
7. 7. Thixotropic rubbers solutions (see Table 7)

The manufacture of black rubber tyres etc., uses carbon black. When dispersed, the particles
are attracted to one another, and form a network throughout the rubber solution. The rubber
solution itself is shear thinning, and the carbon black network also renders a degree of shear
thinning, but it is also thixotropic.
Table 7
Rubber systems
Author(s)
Ref.
Details
Gent and
Alan
Lomov et al.
Katishonok et
al.
White
[91]
Thixotropy in rubbers containing particulate fillers
[92]
[93]
Thixotropy of nitrile rubber system with combined steady-state flow and vibration
Thixotropic for solutions of chlorinated rubber
[94]
Review of thixotropy in carbon-black rubbers
21
Table 8
Food and biological systems
Author(s)
Ref.
Details
Benezech and Maingonnat

Noik et al.
Battistoni et al.
Morris et al.
Baxter
Divjak
[95]
Thixotropy in set, stirred and drinking yoghurts
[96]
[97]
[98]
[99]
[100]
Thixotropy
Thixotropy
Thixotropy
Thixotropy
Thixotropy
of xanthan protein complexes obtained by fermentation

of digested municipal solid-wastes
of acetan and related xanthan gum polysaccharide solutions
of sludge in anaerobic digestors
in xanathan-gum-based low-calorie mayonnaises and salad dressings
7.8. Thixotropic food and biological systems (see Table 8)

M a n y food and biological systems are well known examples of thixotropy. For instance,
stirring yoghurts makes them thinner, but leaving them to rest thereafter thickens them again.
Thixotropy in food thickeners such as xanthan gums can cause problems in that the suspending
properties they give to liquids m a y take time to appear after shearing and this could cause some
initial sedimentation or creaming of suspended material.
7.9. Thixotropic creams and pharmaceuticals products (see Table 9)

Creams and other personal-product and pharmaceutical materials are given 'body' by using
materials--so-called t h i x o t r o p e s - - t h a t happen to be thixotropic. Here the original meaning of
thixotropy as conferring gel-like properties is still very often the controlling idea. The time
effects seen in using these materials are therefore again only o f nuisance value.
7.10. Other thixotropic suspensions (see Table 10)

Some other examples are cited where thixotropy is seen in structured liquids of different
kinds, most of which are flocculated in some way, ranging from flocculation induced by
decreasing droplet size in emulsions through to the deliberate addition of thixotropes.
Table 9
Creams and pharmaceuticals
Author(s)
Ref.
Details
Okor
Junginger
Matsumoto and Nakata
Assmus
Yamamura
[101]
[102]
[103]
[104]
[105]
Effect of phenol on thixotropy of pharmaceutical gels

Thixotropy of cosmetic and dermatological cream bases
Effect of natural waxes on thixotropy of cosmetics
Thixotropy in some gelling cosmetic oils
Natural wax as a thixotrope for cosmetic pharmaceuticals
22
H.A. Barnes /J. Non-Newtonian Fluid Mech. 70 (1997) 1 33
Table 10
Other thixotropic suspensions
Author(s)
Ref.
Details
Ueda
Faitel'son
Nemets et al.
Shul'man et
al.
Veliev and
Abdinov
Stepita
[106]
[107]
[108]
[109]
Thixotropy in fine emulsions produced using a high-pressure homogenizer

Thixotropic properties of epoxy resin polymers
Thixotropy in aluminum and zirconium oxides suspensions
Thixotropy of electrorheological suspensions
[110]
Thixotropy in magnetically active (ferromagnetic dust) liquids
[111]
[112]
[113]
[114]
Alkali metal silicates and montmorillonite as thixotropes in limestone-based plaster

Thixotropy in silica(Aerosil)-based adhesives
Thixotropes (silicas, calcium carbonate or PVC) in unsaturated polyester resin
Aerosil as a thixotrope
[115]
Effect of electrolyte on thixotropy in ceramic slips
[116]
[117]
Effect of additives on aqueous poly(vinyl alcohol) thixotropy

Development of thixotropy in metal alkoxide solutions undergoing hydrolysis and condensation reactions.
Thixotropic in silicate suspensions
Ito
Gao et al.
Arima and
Eguchi
Kruger and
Hulsenberg
Fedotova
Sakka and
Kozuka
Tretinnik
[118]
7.11. M o r e e x a m p l e s in detail
It is interesting to select a group of recent papers to study their different approaches. R a m s a y

and Linder [119] studied montmorillonite c l a y - - a naturally occurring clay from C r o o k County,
W y o m i n g USA. The size of these clay plates is considerably bigger than Laponite and their
shape is less well defined. Using small-angle neutron scattering (SANS), they showed that under
shear, the short-range interactions disappeared. They showed that the anisotropic structure
brought about by shearing remained for m a n y hours, even days, after the shear was removed.
This was in accord with their G' measurements. These showed that the structure built up quickly
while the particles were still aligned. It took a long time before complete isotropy was achieved.
They suggest that montmorillonite is well described by this explanation, but the breakup of flocs
is a more likely explanation in Laponite with its smaller plates. Thus, the montmorillonite
samples are more thixotropic. The rebuilding is driven by Brownian forces which take longer to
align larger particles like montmorillonite. They also note in passing that the linear elastic limit
moves to higher shear.
Zhang and Nguyen [120] used a technique to measure the rebuilding of the yield stress for
mayonnaise that relied on the position of apparent cessation of flow in a wide-gap concentric
cylinder apparatus. U p to 1000 s was needed before the yield-line came to a constant position.
Takeeshi, Wei and Sato [121] studied the thixotropic response of fumed silicas (Aerosil 200
and OX 50) suspended in polybutadientes of various viscosities (1, 11, 33 Pa s). After shearing,
the normal network structure rebuilds slowly, with considerable differences still occurring at 8
h, but interestingly if a 15% strain was imposed for even 2 min, the structure became stiffer still
from rest. This is an example of a shear-enhanced flocculation if the shear is limited.
23
Breton-Dollet et al. [122] measured the thixotropic behaviour of maize starch pastes using a
loop-test method, noting the area under the curve as a measure of thixotropy. It remained fairly
constant as a function of temperature for the first loop for maize, but was lower and thereafter
decreased significantly as a function of temperature for the second and third loops. Unfortunately in this case, no attempt seems to have been made to establish any equilibrium data. For
waxy starch pastes, the thixotropy was lower and a decreasing function of temperature and the
number of loops. The difference in behaviour was attributed to the presence of amylose and
amylopectin in the maize starch.
Berland and Launay [123] examined the thixotropic behaviour of wheat flour doughs and
showed that thixotropic effects are seen in flows other than steady shear. They measured the
thixotropic recovery of the storage modulus measured in the linear region (0.2% strain) after
straining at higher strain amplitudes in the nonlinear region. Recovery is complete--although
taking many minutes--up to large amplitude stains of around 20%. Above that value,
irreversible changes seemed to occur.
7.12. Blood
Thixotropy in blood has been recognised for a long time, but a major problem encountered
in investigating restructuring of individual blood cells into aggregates called rouleau is that
sedimentation takes place quite quickly as the aggregates form. Hence the full potential of
restructuring is not always seen. Of course the circulation takes blood through many flow
regimes, and the breakdown and recovery of structure is important especially in blood sensitive
to aggregation. A general review on the experimental work on human blood viscoelasticity and
thixotropy was presented by Stoltz and Lucius [124], who showed that some models used for
polymer solutions could also be used to account for the phenomena observed with blood
(transient and periodic flow). Being more specific, Huang et al. [125] studied the effect of
haematocrit (red cell concentration) on thixotropic parameters. They found that the rate
constant of thixotropy--in this case arising from the breakdown of rouleuax into individual red
cells--was independent of the haematocrit.
8. Mathematical theories
8.1. Requirements o f useful models
The ideal model to describe thixotropic behaviour would start from the fact that some
fundamental, rheology-determining physical entity takes time to change when the flow field
around it has changed or is changing. As we have already said, this might be for example the
size of a floc; the orientation angle of an alignable particle or the density of transient
entanglements. In the simplest models, all such fundamental parameters change instantly with,
for instance, shear, shear rate or shear stress. First we have to know at what rate these changes
take place, and then if we know how the microstructure relates to the stress, we can predict the
overall behaviour. Most workers in this field have used theories to describe viscous thixotropic
phenomena, and only a few have attempted to describe viscoelastic effects. Representative
examples of classes of theories are described below and others in that field are noted.
24
8.2. Viscous theories

Current theories for thixotropy fall into three groups: first those that use a very general
description of microstructure described by a numerical value of a scalar parameter, typically 2,
and then use d2/dt as the working parameter; second those who attempt some direct description
of the temporal change of microstructure as for instance, the number of bonds, or an attempt
at describing real floc architecture using fractal analysis, and third those that use the viscositytime data itself on which to base a theory.
8.2.1. Indirect microstructural theories

Most workers in this area have developed mathematical theories of thixotropy based on the
numerical scalar measure of structure, often designated by 2. Using this simplistic cypher,
completely built structure is represented by 2 = 1 and completely broken-down structure as
2 = 0. In the simplest case of a typical, inelastic, non-Newtonian liquid with upper and lower
Newtonian viscosity plateaus, 2 = 1 corresponds to t/o and 2 = 0 corresponds to t/a, with points
between taking intermediate values.
Then thixotropy is usually introduced via the time derivative of the structure parameter,
d2/dt, which is given by the sum of the buildup and breakdown terms, which, in the simplest
theories, are only controlled by the shear rate and the current level of structure 2. The most
general description of the rate of breakdown due to shearing is given by the product of the
current level of structure and the shear rate raised to some power, and the driving force for
buildup as controlled by the distance the structure is from its maximum value, i.e., ( 1 - 2),
raised to another power. Then
d2
= g(~, 2) = a(1 - 2) h - c2~ d,
(5)
where a, b, c and d are constants for any one system. If the value of g(~, 2) is negative, the
system is breaking down towards equilibrium; if it is positive, it is building up towards
equilibrium. At equilibrium, for every value of ~ there is a particular value of 2 which in this
equation is found by setting d,~/dt to zero.
Godfrey [4] has summarised the development of these two-process models beginning with
Goodeve and Whitfield in 1938 [126] which led to an earlier version of the above equation due
to Moore [127] with both b and d as unity, and progressing through Cheng and Evans [128] who
made b unity, but allowed d to be non-unitary, through to the very general 'structural kinetics'
model of Mewis, with both powers taking non-unitary values. This latter formulation was also
used by Lapasin's group [129]. The next step in this kind of approach is to relate the structure
2 - - a s calculated using the equations a b o v e - - t o the stress tr or viscosity ~/ in some flow
equation. As we shall see this has been done in a variety of ways which ranged from a simple
Bingham equation, through the Cross model to a Cross-like model containing a yield stress.
Most of the differences between the theories in this area are accounted for in the various
combinations of these structure change and structure-viscosity formulations.
Baravian, Quemada and Parker [130] recently proposed a modification of the Cheng and
Evans approach. Their study is worth looking at in detail for two reasons. First it follows the
tradition route to describing thixotropy, and second, it shows how long and seemingly involved
the procedure to describe thixotropy becomes.
25
They postulate that the relationship between viscosity and structure is given by
q(0-, t) = q(2) = (1
K2)2 ,
-
K= 1 -
\rio /
(6)
where % and ~/~ are the usual limiting values of viscosity at very low and very high shear
rate/stress, respectively. This assumes that the effect of stress on the viscosity is also accounted
for within the current value of the structural parameter 2, which can itself be written as
where q is the current value of viscosity. Then for any system one has to find the values of %
and r/~ (and thus, K), and from these, all values of r/can be converted into values of R. They
found that the relationship between the equilibrium value of the structural parameter 2 and the
shear stress 0- was given by
Requit(0- )
~---
[1 -I- (0-/0-c)p] --1
(8)
From any one particular equilibrium position of stress, 1 Pa jumps were made up and down
and plots of dR/dt versus R were made. These were of the form
dR
1 ~1
(9)
This kind of curve was obtained for many values of equilibrium stress. The values of the
constants were then described by the equation:
R(t) = Requi~+ (2ini- 2eq,i0exp - t/ta2equi~
(10)
Thus, for all values of stress, they could now define 2in~, Requil and 6. Using the stress-up as
well as stress-down data, the values of 6 were the same as a function of stress. This theory was
able to describe a loop test very well, once instrument inertia had been accounted for.
Other variations on this theme include that of De Kee et al. [131], (following Tiu and Boger
[132]), who described the break-down behaviour of various food systems by
dR
dt
--
c~'d(R
--
Requil)n.
(1 1)
The viscosity was described by a multiple exponential-type flow law

0(9) = R(0-o+ 9Zr/i,e- 'P~).
(12)
The theory was used to characterise viscosity decay curves for yogurt and mayonnaise.
8.2.2. Direct structure theories
Denny and Brodkey's applied reaction kinetics to thixotropy via a simple scheme that looked
at the distribution of broken and unbroken bonds [133]. The number of these bonds was later
linked to viscosity. The forward and reverse rate constants k'~ and k2 represented the breakdown
kinetics in flow, and the buildup kinetics, see for instance van den Tempel [134] who related
bonds to flocculated system of fat globules. Denny and Brodkey wrote down the rate of
structure breakdown as (cp. Ruckenstein and Mewis [135]):
26
H.A. B a r n e s / J . Non-Newtonian Fluid Mech. 70 (1997) 1 - 3 3
d(unbroken)
- kl(unbroken) n - k 2 ( b r o k e n ) m,
dt
(13)
and solved to give the viscosity by assuming it is linearly proportional to the amount of
unbroken structure, with a maximum value when completely structured of r/o and a minimum
value when completely destructured of r/~. The rate constant k2 is assumed to be independent
of shear rate, being merely a description of Brownian collisions leading to restructuring, while
the rate of breakdown constant is related to shear rate by a power-law expression.
The way the well-known Cross model was derived is instructive [136]. Assuming that a
structured liquid was made up of flocs of randomly linked chains of particles, Cross derived a
rate of equation of the form:
dN
dt
= k 2 P - (ko + kl~)m)N,
(14)
where N was the average number of links per chain, k2 was a rate constant describing Brownian
collision, ko and kl were rate constants for the Brownian and shear contributions to breakdown, P was the number of single particles per unit volume, and m was a constant less than
unity. At equilibrium d N / d t is zero, so
N~=
k2P
(
k,
)"
ko 1 +~o~) m
(15)
Then assuming that the viscosity was given by a constant, r/~ plus a viscous contribution
proportional to the number of bonds Are, he derived his well-known relationship:
F/e -- r/a, _
1
k
r/o r/~ 1 + ~ l7
(16)
"m
Cross could of course have used the non-equilibrium data to derive a thixotropic model as
later others did using his model.
Lapasin et al. [137] used a fractal approach to describe flocculated suspensions. The analysis
of fractal flocs using computer simulations based on the ballistic, cluster-cluster aggregation
mechanism suggested that Cfp in Quemada's model, i.e., 2/[q]Om in the K D equation, is given by
Cfp=
B + A (N~+x I - 1)
B + Nmax - 1
(17)
where A and B are constants, Nmax is the number of primary particles in a floc, and fl is given
by 3 / D - 1, where D is the fractal dimension of the floc. Then Lapasin et al. argue that (cf.
Cheng and Parker)
dNm,x
- - a ( N - Nmax) - b~rP(Nmax - - Nmax~)
dt
(18)
where Nmax.~ is the lower limit to which Nmax tends as the shear stress o- becomes infinite; a, b
and p are material constants. This can be solved for N >> Nmax to give

aN
Nmax = Nmax,~ + _~_o- 1,
27
(19)
which, once we have replaced the lumped parameter (aN/b) L'p by a critical stress oc and
substituted into the Krieger-Doughery equation, gives
q -(1/2)
--
Lr/~J
qb B + A
=
~bmax
Nm,~x~ + a
/s
BA-Nmax,~+(~--~-~" - - 1
(20)
\o-,./
This equation describes the breakdown of flocs under flow, and predicts a yield stress and a
finite high-shear-rate viscosity. It described very well the behaviour of both TiO2 and mica
dispersions in steady state. (A much more complicated theory of this kind had been proposed
by Eyring much earlier [see [138]]).
8.2.3. Simple viscosity theories
Frederickson [139] formulated an expression for the rate of change of fluidity (the inverse
of viscosity) of a non-Newtonian system as
and used this expression for steady state flow (dO/dt = 0), recovery at rest (?',= 0), the sudden
application of stress and then a loop test. Like the Cross model, this model also has higher and
lower Newtonian plateaus at equilibrium, and if the quadratic dependence on shear-rate is
replaced by a power-law relationship, they become similar.
Mewis and Schryvers [28] have recently devised a theory that also circumvents the use of any
structural parameter such as 2, and instead used the viscosity as a direct measure of structure.
They proposed that the rate of change of viscosity rather than rate of change of structure be
related to the viscosity difference between the steady state and current values of viscosity (not
the structure difference), respectively, viz:
dq
d t - K[~/s(~")- r/]"
(22)
This integrates to give

q = q ..... - [r/e,~ - r/e,O][(q - 1)Kt(r/e -s_
qe,0)n-1 + 1] ''(l --")
(23)
Mewis and Schryvers then made the (Newtonian) assumption that r/e,0= r/i,~ which makes the
use of the equation simpler since it is much easier to measure the eventual viscosity of the initial
steady state condition. This assumes that the viscosity at the end of the initial steady-state period
is the same as that at the beginning of the new shear-rate test, i.e., that the system is essentially
Newtonian between those conditions. This is reasonable under some conditions but as Mewis's
previous work has shown, it is only strictly true for most systems at higher shear rates. Using
a value of n of 5/3, they fitted experimental data very well for carbon black in mineral oil.
Kristensen et al. [140] modelled the thixotropic breakdown behaviour of maize starch pastes
using the equation:
H.A. Barnes,/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33
28
( J / - qoo)' -m = [(m -- 1)kt + 1]0/0 - qoo)' -m
(24)
where r/0 and qoo are the asymptotic values of viscosity r/ (representing the fully structured
and fully destructured states, respectively) measured at time t any particular shear rate, and k
and m are material constants. This approach had been used with previous success for
minerals and industrial suspensions (see [141]). For the starch paste studied they found that
the data was satisfactorily described by m = 3, thus suggesting a third-order kinetic model.
Over the shear rate range tested, the steady-state flow curves could be described by a
power-law model with an approximate half-power.
8.3. Viscoelastic theories

Almost any viscoelastic theory can have thixotropy introduced if the particular parameters
that give the viscous and elastic responses are made to change in the way we have described
for purely viscous behaviour. Probably the best example of this approach is given by the
model due to Acierno et al., [142] who considered a model based on a series on Maxwell
elements. These papers have had a large influence in the field, and have already been cited 49
and 104 times respectively at the time of writing. The number of elements in their model was
such that they could be represented by a continuous spectrum. Simplifying the model to a
discrete series, it is possible to write down the behaviour as
a = Z,a,,
~ + O, d t \ O J = 0;i
(25)
where a~ is the stress, G~ the modulus, and 0 the relaxation time ( = ~Ii/G~ and labelled 2g in
their paper) of the ith element in the discrete spectrum.
Thixotropy is introduced via the well-used structure parameter 2 (labelled as x; in their
paper):
G~= Go,2;,
0~ = 00,2] '4
(26)
The rate equation is then given by
a ,FE,
i
dt
0i
0i L6;]
(27)
where Ei is the instantaneous elastic energy in the ith element. This is the same as the Moore
linear model, except that now ~ is replaced by the generalised expression (E/Gi)~/2/Oi that
accounts for the elasticity as well as the viscosity. The theory gives an excellent description
of most of the rheological behaviour of a low-density polyethylene melt in shear and extensional transient and steady-state flow. The model is equivalent to the Moore model if
reduced to the viscous case. Shoong and Shen [143] introduced a power-law dependence of
the breakdown term which then compares with the Cheng and Evans' inelastic model. An
obvious extension is to raise both terms to non-unitary powers.
29
9. The break-down and build-up of isolated flocs

The two key mechanisms of thixotropy for typical systems are floc erosion and Brownian
collisions. Work has been published on these topics for diluted flocs and it is instructive to relate
these studies to thixotropic build-up and breakdown of suspensions of flocs.
The diffusion rate of isolated flocs decreases significantly as their size grows. Reynolds and
Goodwin [144] measured the diffusion coefficients of isolated flocs and found a rapid decrease
of diffusion rate with floc size, with the particular value depending on the floc geometry which
they studied as linear or clustered flocs. As these are quite moderate floc sizes, it is obvious that
very large flocs of hundreds or thousands of primary particles will move very sluggishly. The
effect of primary particle size on translational diffusion coefficient was worked out by Einstein
who showed a simple inverse dependence on size. However the rotational diffusion of particles
scales as the inverse cube of particle size (see [145]). This behaviour explains why exponentialtype expressions for rebuilding contain a driving force such as (1 - 2), because rebuilding starts
at a given floc size that grows and then the diffusion coefficient decreases. This means that
collisions become less frequent, and as rebuilding progresses it gets slower and slower, but
theoretically never stops.
The breakdown of isolated flocs in imposed shear fields has been studied by a number of
workers. Sonntag [145] has summarised the results as dr = c~ ~ where g has been measured as 0.2
or 0.5. The surface shear stress experienced by an isolated floc is given by dfdqp, where dr is the
floc size, d the size of the primary particles, t/the viscosity of the continuous phase and ~ is the
shear rate. It is this stress which produces surface erosion of primary particles if it is greater than
some bond shear strength between the primary particles [see Mtihle [146]]. This expression shows
that floc breakdown in a given shear field is fastest for the largest sized flocs, i.e., at the shortest
times, as well as being proportional to the shear rate raised to a power. These facts are reflected
in the structure breakdown criteria normally used, d2/dt Qc - 2 . ~ ",n.
I0. Overall conclusions

Thixotropy comes about first because of the finite time taken for any shear-induced change in
microstructure to take place. The microstructure is brought to a new equilibrium by competition
between the processes of tearing apart by stress and flow-induced collision, in a time that can be
minutes. Then, when the flow ceases, Brownian motion is able to move the elements of the
microstructure around slowly to more favourable positions and rebuild the structure. This can
take many hours to complete. The whole process is completely reversible.
The position of various areas of thixotropy today is well summarised by three quotations:
(1) As to the proper understanding of the word itself, we can do no better than quote from
Lewis Carroll's Alice in Wonderland, "When I use a word," Humpty Dumpty said ... "it means
just what I choose it to mean--neither more nor less". "The question is", said Alice, "whether
you can make so many words mean so many different things".
(2) As to the state of experimental investigation in thixotropy, we quote Godfrey [4],
"Thixotropy is one of the more complex characteristics associated with the behaviour of
non-Newtonian liquids ... most of the available [experimental] data leave something to be
desired".
30
(3) Then to assess the state o f proper theoretical u n d e r s t a n d i n g of thixotropy, particularly in

viscoelastic systems, " T h e results obtained so far do n o t allow [sic] to consider the modelling o f
the thixotropic viscoelastic b e h a v i o u r as a solved p r o b l e m " , L a p a s i n a n d Pricl [16], but see [147].
Thus, we conclude that there is plenty o f scope for m o r e w o r k in these three areas; viz, a fuller
definition, a better collection o f d a t a on well-characterised model systems a n d then the need for
a comprehensive t h e o r y that describes b o t h viscous a n d viscoelastic thixotropic effects: c o m p u tational efforts such as molecular modelling will be very i m p o r t a n t in such studies because o f the
large n u m b e r o f variables t h a t would ensure, as will the i n t r o d u c t i o n of t h i x o t r o p y into C F D
codes.
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Jear~lof

J. Non-Newtonian Fluid Mech., 70 (1997) 1-33

Unilever Research Laboratory, Bebington, Merseyside L63 3JW, UK

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

Completelystructured- giving ~)~4?>'ft'~,/~--T:~--~.~_2LI

Partly structured - giving

Fig. 1. Breakdown of a 3D thixotropic structure.

H.A. Barnes / J. NonNewtonian Fluid Mech. 70 (1997) 1-33

2.3. How is" thixotropy generally understood today7

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

McGraw-Hill Dictionary of Scientific and Technical Terms [20]--"Property of certain gels

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

3. Description of the phenomenon

3.2. Typical behaviour

H.A. Barnes//J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

Fig. 3. Two kinds of step experiment.

shear rate (log scale)

H.A. Barnes /J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

Oyo + [try -- or](1 -- e-~t/~))

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

inelastic, viscous response

H.A. Barnes /J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

5. Typical thixotropic experiments

H.A. Barnes / J . Non-Newtonian Fluid Mech. 70 (1997) 1-33

5.2. Start-up experiments

shear rate, 1/s

H.A. Barnes /J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

5.3. Artifacts involved in measuring thixotropy

H.A. Barnes / J . Non-Newtonian Fluid Mech. 70 (1997) 1-33

6. Engineering consequences of thixotropy

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

7. Examples of systems and studies from the literature

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

Effect of thixotropy on film formation

Thixotropy in urethane modified alkyd resins

Effect of thixotropy on thick film screen printing

7.4. Thixotropic oils and lubricants (see Table 4)

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

Thixotropy of montmorillonite dispersions

Effect of vibrations, electrolytes and temperature on thixotropy of clays

Effect of electrolyte and various colloids on thixotropy of bentonite clay suspensions

Orientation-thixotropic effect in aqueous dispersions of montmorillonite clays

Review of modified Bentonite (organoclay) organophilic thixotropes for coatings

Effect of Bentonite on storage properties of chlorinated rubber enamels

7.5. Thixotropic coal suspensions (see Table 5)

suspensions show considerable thixotropy, and problems

Thixotropic properties ester-based synthetic lubricating oils

H.A. Barnes / J . Non-Newtonian Fluid Mech. 70 (1997) 1-33

and physical stability of coal slurries

Thixocasting--a casting process for near-net-shape manufacture aluminium alloys

7.6. Thixotropic metal slushes (see Table 6)

7. 7. Thixotropic rubbers solutions (see Table 7)

Thixotropy in rubbers containing particulate fillers

Review of thixotropy in carbon-black rubbers

H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33

Benezech and Maingonnat

Thixotropy in set, stirred and drinking yoghurts

of xanthan protein complexes obtained by fermentation

7.8. Thixotropic food and biological systems (see Table 8)

7.9. Thixotropic creams and pharmaceuticals products (see Table 9)

7.10. Other thixotropic suspensions (see Table 10)