Trix Otro Pia

ELS EVI ER J. Non-Newtonian Fluid Mech.
, 70 (1997) 1-33
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Thixotropy a review
Ho wa r d A. Ba r n e s
Unilever Research Laboratory, Bebington, Merseyside L63 3JW, UK
Received 16 November 1996; received in 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, microstruc-
tural 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
Th e gr owi ng use o f c l a y- ba s e d s t r u c t u r a n t s t o g e t h e r wi t h t he i ncr eas i ng pr e s e nc e o f f l occu-
l a t e d s t r uc t ur e s i n h o me , p e r s o n a l a n d c he mi c a l p r o d u c t s a n d pr e c ur s or s has l ed t o t he
a p p e a r a n c e o f t h i x o t r o p y in a wi de ni ng r a nge o f s i t uat i ons , qui t e a p a r t f r o m its pr e s e nc e i n
s ys t ems l ong k n o wn t o di s pl ay t he p h e n o me n o n . Di f f i cul t i es t he n ar i se i n mi xi ng a n d h a n d l i n g
t hes e ma t e r i a l s be c a us e t h i x o t r o p i c s t r uc t ur e s pr ogr es s i vel y b r e a k d o wn o n s he a r i ng a n d sl owl y
r e bui l d at rest . Th e t i me- s cal es i nvol ve d c a n r a nge f r o m ma n y mi nut e s i n t he case o f b r e a k d o wn
t o ma n y h o u r s i n r ebui l di ng.
0377-0257/97/$17.00 1997 Elsevier Science B.V. All rights reserved.
PII S0377- 0257( 97) 00004- 9
2 H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33
Thixotropy has been deliberately built into products to make t hem usable by non- exper t s- -
with the best-known example being thixotropic pai nt s- - 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 unwant ed
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 wort h consulting for interesting examples of thixotropic
systems not cited here.
2. A history of thixotropy
2.1. Origins
In 1923, Schalek and Szegvari found t hat aqueous iron oxide "gels have the remarkabl e
property of becoming completely liquid t hrough 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 wi t hout 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).
Al t hough no ment i on 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] devot ed to the subject, having
been the first to introduce it into the title of a paper when he described the flow properties of
al umi ni um hydroxide gels. Freundlich and co-workers soon found thixotropic effects manifested
by a whole variety of systems including vanadi um 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 woul d melt on heating and t hen 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 t hi xot ropy 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
H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33 3
edition of this book published in 1949, nearly 120 papers on t hi xot ropy 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
t hem whet her t hi xot ropy ought to be studied at const ant rate of shear or at const ant stress? This
is still a most controversial question.
Scott-Blair quotes Hamaker ' s expl anat i on of t hi xot ropy as being due to the secondary
mi ni mum so t hat ' particles can form a loose association which is easily dest royed by shaking but
re-establishes itself on standing' . This explanation still stands. Wi t h our present knowl edge of
mi crost ruct ural changes, it is probabl y safe to say t hat all materials t hat are shear t hi nni ng are
thixotropic, in t hat they will always take a finite time to bring about the rearrangement s needed
in the mi crost ruct ural elements t hat result in shear thinning. As Scott-Blair concl uded all those
years ago "I f this recovery is very rapid, the phenomenon is observed as structural viscosity
[shear thinning]; if slow, it is observed as t hi xot ropy". However even Scott-Blair sometimes
confused t hi xot ropy with shear thinning, as in his example of the i mport ance of t hi xot ropy for
drilling muds t hat must be r unny [sic] when lubricating the drill, but " of a high enough
consistency at rest to avoid settling of suspended mat t er".
An i mport ant point he made concerned a suggestion t hat certain results of flow in capillary
tubes of suspensi ons- - t hat we now believe showed mi grat i on of particles away from the wall
and thus, have an easier flow in small rat her t han large t ubes - - was due to thixotropy. He
refuted this by showing t hat doubl i ng 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 t hi xot romet er [12]. He not ed t hat "It is a well-established fact
t hat t hi xot ropy is more pr onounced in systems cont ai ni ng non-spherical particles", this is
obviously so because they have to find themselves in the best 3D structure by rot at i on as well
as movement , and progress from a solid gel to a freely flowing liquid due to complete
mi crost ruct ural breakdown, see Fig. 1.
Thi xot ropy is one of the few original technical terms used in pre-war, Eur opean rheol ogy
circles t hat has survived, unlike ' structural viscosity' (Strukturviskositaet, whi ch we now
underst and as shear thinning) and 'false body' (now underst ood as extreme shear t hi nni ng with
thixotropy) whi ch 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] t hat recovered quickly, while the thixotropic material takes some times before
relatively fast recovery takes place. Today we underst and t hat they are bot h manifestations of
thixotropy. False bodies were taking a long time to die.
Jobling and Robert s in 1957 [14] comment ed t hat "t hi xot ropy now has an even less distinct
connot at i on. Electronic met hods of measurement have shown t hat the time-lag required before
Re a de r s wi t h an i nt er es t i n t he hi s t or i cal de r i va t i on of sci ent i fi c expr es s i ons ar e di r ect ed t o Scot t - Bl ai r [10], p. 52.
Al l Scot t - Bl ai r ' s books wer e wr i t t en as per s onal me moi r s a nd ar e ver y evocat i ve of t he ma n hi ms el f f or t hos e who
knew hi m.
4 H. A. Bar ne s / J . Non-Newtonian Fluid Mech. 70 (1997) 1- 33
the original structure is regained may be very short indeed and it t hen 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
i nst ant aneous rate of shear. The latter effect is frequently called ' structural viscosity' ". They
went on to say "We endorse Pryce-Jones' s plea t hat in the absence of aut hori t at i ve definitions,
terms such as ... t hi xot ropy shoul d not be used unless the i nt ended meani ng is made clear". In
the Discussion section of this paper, Marcus Rei ner notes t hat ' structural viscosity' and
' t hi xot ropy' are seen as the same thing by some, with structural viscosity seen as a material with
"nearl y zero time of recovery".
The full extent of t hi xot ropy was mai nt ai ned by Bauer and Collins in their 1967 review [1]:
"When a reduct i on in magni t ude of rheological properties of a system, such as elastic modul us,
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 t hi xot ropi c". They went on
to say t hat t hi xot ropy was "usual l y conceived as an unusual propert y of very special materials,
sol-gel systems such as aqueous iron oxide dispersions, t hi xot ropy in the sense described above
has been found to be exhibited by a great many and a large variety of systems. Al ong with the
breakdown in structure, ot her non-rheol ogi cal features change, such as conduct i vi t y and
dielectric const ant ". Lastly they not ed t hat "The terms used by Freundl i ch are now seen to be
archaic, viz liquefaction, re-solidification, sol. These had some obvious meani ng for the
qualitative changes brought about in low concent rat i on dispersions of highly insoluble oxides of
needle-like crystals such as i ron oxide and vanadi um pentoxide in low-viscosity aqueous medi a".
Nowadays t hi xot ropy is sometimes used to include all time effects in a movement to
non-l i near behaviour, see for instance Cheng [15], but especially Lapasin and Pricl [16], who
illustrate thixotropic behavi our by the transient response of viscosity and normal force of
S~KING / S ki, , .
. . . . / e
Completely structured- giving ~ ) ~ 4 ? > ' f t ' ~ , /~ - - T : ~ - - ~ .~ _ 2 L I ~ ' ~ - ' ~ ' A ~ " ~ / / ~ \ ~ , ~ , , V ~ f '
e l a s t i c , s o , d - , k e r e s p o n s e . " I I . " / .
Partly structured - giving '-....._~" ~-~'~- y t ~ f ~ / t / ~ - " ; I
" - k viscoelastic r e s p o n s e i / , ~ ' ~ / - " ~ / ' , . - , ~ - . , ~ # ~ ~ " ~ ~ , ~ ~i
Completely unstructured
~ ' ~ / 4 ~ ~ - giving vi scous, shear
-thinning r esponse
Fig. 1. Br eakdown of a 3D t hi xot r opi c st ruct ure.
H.A. Barnes / J. NonNewtonian Fluid Mech. 70 (1997) 1-33 5
pol ymer solutions. They t hen not ed t hat the stress overshoot on start-up increases with
increasing rest time. This is an interesting poi nt - - bui l d up in pol ymer solutions is usually
consi dered to be rapid, and rest times are rarely considered necessary. Weakl y cross-linked gels
woul d give the same thixotropic effect as a flocculated system.
2.3. How is" thixotropy generally understood today7
One of the first definitions of t hi xot ropy was given by Freundl i ch and Rawi t zer [17] who
stated t hat "By t hi xot ropy is meant the phenomena of concent rat ed gels ... whi ch solidify to gels
which may again be liquified to sols. The resolidification occurs repeatedly, at const ant
t emperat ure with a const ant speed". (This woul d be very far from the ki nd of definition offered
today. ) However, Pryce-Jones [11] soon afterwards stated t hat the true meani ng of t hi xot ropy
was "an increase of viscosity in a state of rest and a decrease of viscosity when submitted to a
const ant shearing stress".
It is clear t hat people using the word t hi xot ropy t oday fall into two camps: first those who
underst and it in the latter (Pryce-Jones) sense as the time response of the mi crost ruct ure 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 t hos e- - of t en in industrial ci r cl es - - who underst and t hi xot ropy in its
original Freundl i ch and Rawi t zer sense, as stated above, of conferring gel-like properties to a
liquid which di sappear on shaking but reappear on standing. This part i cul ar propert y adds
considerable advant age to the practical use of materials such as paints, adhesives and coatings.
Unless this different use is borne in mi nd, severe mi sunderst and will arise on reading the general
literature. The former group woul d underst and the use of t hi xot ropy by the latter group as
conferring extreme shear t hi nni ng to a liquid by, for instance, the addi t i on of so-called
thixopropes or by i nduci ng flocculation. On the ot her hand the latter group only see the
t emporal properties of t hi xot ropy 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 t hat t hi xot ropy has, on occasions, been confused with shear thinning.
There are various definitions of t hi xot ropy offered in the current general scientific literature,
e.g., scientific dictionaries and encyclopedias, t hat reflect these two points of view. Some are
misleading, with even the best being incomplete. The following are a selection t hat illustrate the
situation:
Oxford Encyclopedic Di ct i onary of Physics, [ 18] - - "Thi xot r opy: 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 propert y is
particularly associated wi t h 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 Di ct i onary of Science and Technol ogy [ 19] - - "Rheol ogi cal propert y 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 propert y of paints, because it makes for a thick film whi ch
is nevertheless easily wor ked. "
McGraw-Hill Dictionary of Scientific and Technical Terms [ 20] - - "Pr oper t y 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 Nost rand' 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 mot i on within
the fluid. The viscosity usually decreases with the length of time the fluid has been in motion.
Such systems commonl y are concent rat ed solutions of substances of high molecular weight, or
colloidal suspensions."
Oxford Concise Science Dictionary [ 22] - - "Mor e 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 nondri p paints (which are more
viscous on the brush t han on the wall) and lubricating oils (which become t hi nner when the
parts they are lubricating start to move). "
Chambers 20th Century Dictionary [23]--"Thi xot ropy: the property of gels of showing a
t emporary reduction in viscosity when shaken or stirred."
Definitions given in more specialised dictionaries emphasise the time aspect of thixotropy:
Polymer Technology Dictionary [24]--"Thi xot ropy. 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] - - "Ti me- 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 Rheol ogy was quot ed by Rei ner and Scott-Blair in 1949 [26] as having
defined thixotropy as "t hat property of a body by virtue of which the ratio of shear stress to rate
of deformat i on [viscosity] is temporarily reduced by previous deformat i on". Some time later
thixotropy was defined as "a comparatively slow recovery, on standing, of the consistency lost
t hrough shearing". However, thixotropy has recently been defined by Barnes, Hut t on 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 phe nome non- - a better description woul d 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 popul ar 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 bot h considerable shear t hi nni ng (i.e., gel-fluid transition) and also time changes over and
above those encount ered when in its structured state the thixotropic material mi ght be
viscoelastic with its at t endant 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 t aken to move from any one state of microstructure to anot her and back again, whet her
from different states of flow or to or from rest. The driving force for microstructural change in
flow is the result of the compet i t i on between break-down due to flow stresses, build-up due to
in-flow collisions and Brownian mot i on. Brownian mot i on is the r andom thermal agitation of
atoms and molecules that results in elements of the microstructure being constantly bombarded,
which causes t hem to move to a favourable position where they can- - gi ven the necessary
attractive f or ce- - at t ach themselves to ot her parts of the microstructure. Very occasionally
situations arise where existing weakly attached microstructural el ement s - - br ought together by
collision duri ng s hear - - ar e slowly t orn apart by the constant action of the r andom Brownian
mot i on. In t hat 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 ent angl ement density or molecular associations in pol ymer solutions. All
these determine the level of viscosity and elasticity, and they all take time to change from one
state to anot her under the action of shear and/ or Brownian forces. In these cases, the maxi mum
microstructure is seen when alignment and spatial distribution are r andom (in three dimensions)
and ent angl ement density is at a maximum. Both these condi t i ons result in the greatest viscous
(and usually elastic) response. On the ot her hand, mi ni mum microstructure is when there is
maxi mum alignment with the flow of fibres; the drop or particle spatial distribution is
asymmetrical in the flow direction, or there are a mi ni mum number of entanglements or
associ at i ons--al l these leading to mi ni mum 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 t han breakdown.
8 H. A . B a r n e s / J . N o n - N e w t o n i a n Fl u i d Me c h . 70 ( 1997) 1 - 3 3
+, a
0
....................... e q u i l i b r i u m .............................................
0 shearing time
Fig. 2. Shearing a thixotropic liquid after short and long rest times.
3.2. Typical behaviour
I f we place a thixotropic material into a viscometer (see Fig. 2) and apply a const ant shear
rate, the measured viscosity will decrease with time, but it will eventually steady out to a
const ant value. If we then switch off the shear and allow the mat eri al to rest for a long time
(without drying or any ot her artifacts such as sedi ment at i on or separation occurring), and
switch the shear on again, the measured viscosity will be initially higher, but it will t hen again
decrease and end up at the same value as t hat which was seen after the original long-term
shearing. However, the level for the original value will not necessarily be the same, because t hat
will depend on how carefully or vigorously the material was initially l oaded into the viscometer
and how long it was left to rest before shearing.
If on the ot her hand a t hi rd experiment is performed where the material is allowed to come
to equilibrium and t hen allowed to rest for the same time as before, the results will be identical.
If now, after equilibrium is achieved, the shear rate is i nst ant aneousl y decreased to a lower
value, the measured shear stress drops instantly, but thereafter it will slowly increase t owards a
new equilibrium.
(If instead of applying a given shear rate we applied a part i cul ar shear stress, then the inverse
appl i es - - t he shear rate woul d increase as the structure breaks down and the change to anot her
(lower) shear stress will result in a sudden decrease in shear rate followed by a furt her drop, see
Fig. 3.)
If we now enquire what is happeni ng on a microscale, we can imagine the picture presented
in Fig. 4, where the viscosity/shear-rate behavi our of a typical thixotropic material (which for
the sake of ar gument coul d be a flocculated suspension) is presented. We start from poi nt a
where the mi crost ruct ure 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 pri mary particles.
We now imagine anot her experiment where the shear rate is increased step-wise from a to end
up at poi nt b. Instantaneously, the floc size will be t hat appropri at e to the shear stress conditions
at poi nt a, but as it experiences the higher shear rate at position a' , it begins to erode, until it
reaches an equilibrium size appropri at e to the higher rate. This process can t ake some time. If
now the opposite ha ppe ns - - t he shear rat e is i nst ant aneousl y decr eas ed- - t he individual particles
H.A. Barnes//J. Non-Newtonian Fluid Mech. 70 (1997) 1-33 9
J~
, T i
STEP EXPERI MENTS
. . . . . . . . . . . . . . . . . v a l u e s - ~
>
T i m e
>
T i m e
. . . . . . . . . . . . - 4_ . . . . . . . 7
~ ~ . ~ equilibrium
Ti me
I
Time
>
Fig. 3. Two kinds of step experiment.
(which gave t he low viscosity) begin to collide and flocculate until t he size of t he floc so- f or med
is appr opr i at e to t he new, lower shear rate. This process also takes time, but t he bui l d-up
proceeds at a di fferent rate t han does br eakdown.
Any concent r at ed suspensi on of particles is shear t hi nni ng, t hus when we consi der flocs, t hey
t oo will show t he phenomena as i l l ust rat ed in Fig. 4. I f we i magi ne t hat t he particles in a floc
are per manent l y gl ued t oget her and t hus, t he floc size is fixed, t he flow curve of such a
suspensi on of fixed-size flocs woul d follow t he lines shown in t he figure accor di ng to t he floc
size. I f t he floc size is now decreased (and t he overall concent r at i on mai nt ai ned) but agai n t he
floc size remai ns unchanged when sheared, t he flow curve will be l ower and (for a given
concent r at i on) t he degree of shear t hi nni ng decreases.
m
o
m
~ 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 i nt erest ed in systems fl occul at ed in a secondary mi ni mum, t he floc
size is not const ant but decreases wi t h i ncreasi ng shear rate (or shear stress). Because t he
viscosity decreases wi t h floc size (see above), we now have a doubl e shear-t hi nni ng effect. Thi s
means t hat flocculated systems are very shear t hi nni ng, see t he equi l i bri um curve in Fig. 4. Thi s
ext reme shear-t hi nni ng also results in such flocculated, t hi xot r opi c syst ems appear i ng to have a
yield stress, since t he stress onl y decreases very slowly as t he shear rate is decreased.
The t rue st eady-st at e behavi our of a t hi xot ropi c liquid is seen bot h after an infinite sheari ng
t i me at any shear rate or shear stress of interest or infinite rest time. Of course, as all these
equi l i bri um states are appr oached asympt ot i cal l y, one comes close t o this state after a reason-
able r at her t han an infinite time, but even t hen, br eakdown times of hour s and rebui l di ng times
of days mi ght be necessary to fully describe a very t hi xot ropi c system.
In a flocculated system, br eakdown is t owar ds an equi l i bri um si t uat i on t hat is gover ned by a
bal ance of hydr odynami c shear stresses pul l i ng st ruct ures apar t by erosi on, and a combi nat i on
of Br owni an and shear forces bui l di ng t he st ruct ure up by collision and accret i on of particles
whi ch aggl omerat e i nt o flocs. The forces hol di ng t he st ruct ure t oget her are col l oi dal in nat ure,
act i ng over shor t distances ( ~ 10 nm) wi t hi n t he composi t e particle. At rest, onl y t he Br owni an
rebui l di ng forces are present , and these are qui t e small compar ed t o t he sheari ng forces, being
of or der 1 kT. Thi s means t hat t he rebui l di ng t i me can be very long, since this small, r andom
force t akes a l ong t i me to rearrange large particles t hat as flocs are get t i ng larger and l arger as
t hey move i nt o a most favourabl e st ruct ure, whi ch is t hen mani f est ed as a hi gher and hi gher
viscosity.
The typical response t o a step-wise change f r om one st eady state condi t i on to anot her is, in
t erms of t he viscosity, oft en charact eri sed by t he so-called st ret ched exponent i al model :
F/ = Y ]e,oQ -~- ( g / e , ~ - - r / ~ , o ) ( 1 - - e - ( t / ~ ) ~ ) , (1)
where r/e,0 is t he viscosity at t he commencement of shearing, ~/e.~ t he viscosity after sheari ng for
an infinite time, z is a t i me const ant and r is a di mensi onl ess const ant (whi ch in t he simplest case
is unity). Thi s equat i on can cope wi t h bui l d-up and br eakdown in st ep-up or st ep- down tests,
wi t h t he values of ~ and r dependi ng on bot h t he level and t he di rect i on, i.e., goi ng f r om 10 t o
1 s - 1 will not have t he same value of f f ound in goi ng f r om 1 t o 10 s - 1. The values of r also
vary wi t h t he condi t i ons of t he test, as well as t he par t i cul ar syst em bei ng tested, and t hey
decrease linearly wi t h t he l og of t he shear rate, typically f r om 0. 7- 0. 9 at l 0 - 2 s - 1 t o 0. 3- 0. 4
at 1 s - 1 in Mewi s' experi ment s [28]. He also showed t hat for a typical flocculated syst em ( f umed
silica in paraffi n oil), z is a decreasi ng f unct i on of r/e.O ~/~/oont, where qcont is t he viscosity of t he
cont i nuous phase, whi ch when t aken i nt o account , pr oper l y describes t he effect of t emperat ure.
(He also report s optical, dielectric and conduct i vi t y results on these systems).
Heymann et al. [29] i nvest i gat ed t he bui l d-up after sheari ng of t he yield stress of five
newspri nt inks, wi t h t he f or mul at i on cont ai ni ng car bon black. A per i od of pre-sheari ng was
carri ed out at 1500 Pa, and t hen t he flow curves were measur ed as a f unct i on of time. For t hose
inks, j udged to have a yield stress ~y, an equat i on similar to Eq. (1) was used to describe t he
rebuilding:
r a t ) = o O y + [ t r y - - or ] ( 1 - - e- ~t / ~) ) ( 2 )
For these mat eri al s so described, t he values of v were f ound to be well over 100 s. For this
reason, it was j udged t hat t he recovery behavi our had no relevance t o t he pr i nt i ng process,
because these process times are of t he or der of a few seconds at most .
Not onl y can shear br eak down or bui l d up flocs, but it can also change their i nt ernal
mor phol ogy. For i nst ance, t he wor k of Mills et al. [30] showed t hat sheari ng freshly pr epar ed
fl occul at ed suspensi ons can densify i ndi vi dual floes, causi ng reorgani sat i on wi t hi n t he flocs. Thi s
shows how i mpor t ant it is t o ' condi t i on' such systems before sheari ng t hem in experi ment s to
el uci dat e their t hi xot r opi c behavi our. They f ound t hat fol l owi ng pr ol onged shearing, loose-
packed flocs became tightly packed and mor e monodi sper sed. Thi s can be i nt erpret ed as a
per manent loss of s t r uct ur e- - r heomal axi s or rheo-dest ruct i on.
The experi ment s of Wol t hers et al. [31] show us how i mpor t ant t hi xot r opy can be in a typical
flocculated systems. They exami ned t he behavi our of a depl et i on-fl occul at ed pol ymer latex
suspensi on and showed t hat t he shear stress dr opped significantly wi t h time, and was still
decreasi ng after 1 h. The values of t he initial and final viscosities t hey f ound were at least an
or der of magni t ude different. They also f ound t hat t he unshear ed sampl es were mor e open flocs
while sheari ng made to fresh flocs mor e dense.
3.3. Antithixotropy
As we have al ready seen, given t he right ki nd of at t r act i on bet ween particles, sheari ng can
pr omot e t empor ar y aggregat i on rat her t han br eakdown, due to t he collision of these at t ract i ve
par t i cl es - - t hi s results in ant i -t hi xot ropy. Dor ai swamy et al. [32] have shown t hat t he average
aggl omerat e size of a suspensi on in shear was given by
r
-- = exp[(8~b~Et)/3Tc], (3)
F0
where E was t he probabi l i t y t hat a collision of particles woul d result in aggl omer at i on, and r and
r0 were t he radi us of t he sheared and unshear ed flocs, respectively. They t hen descri bed an
exper i ment where a 12% phase vol ume suspensi on of i norgani c pi gment in a low mol ecul ar
wei ght pol ymeri c fluid grows f r om 3.4 to 88.1 jam after flowing t hr ough a 50 m l ong t ube of
di amet er 0.038 m. Thi s meant t hat t he value of E was as low as 0.006. They poi nt ed out t hat this
value will t end to zero above a critical stress when t he aggl omerat es begi n to disintegrate. In
separat e experi ment s on a 4 gm glass beads in cor n syrup suspensi on in a cone-and-pl at e
vi scomet er, t hey showed t hat t he aggl omerat e size t ended to a st eady value after sheari ng for
mor e t han about 2 h. Chang and Smi t h [33] showed t hat this ki nd of behavi our is seen in cert ai n
nucl ear waste si mul at e slurries, especially if silica (SiO4) is present .
Ant i t hi xot r opy can also arise because cert ai n floes can become l ooser and mor e open under
t he act i on of shear and t hus t he viscosity increases. One good exampl e of this negat i ve (or anti-)
t hi xot r opy is ferric-oxide suspensi ons in mi neral oil, see [34]. Suspensi ons of acicular, fine
maghemi t e are known to show a st r ong t endency to flocculate due to t he magnet i c propert i es of
t he particles. Li ke ot her such suspensi ons, t here is a range of flow condi t i ons under whi ch
shear-enhanced collisions make st ruct ure rat her t han break it. I n this case t he onset of
ant i t hi xot r opy is ar ound 50 s 1. Below t hat range t he suspensi ons are t hi xot r opi c in t he nor mal
way, while above this critical value, st r ong ant i - t hi xot r opy sets in. They concl ude t hat t he shear
l oosens t he ftocs, whi ch t hen have a hi gher effective phase vol ume.
vi scoel asti c response
~ 4
~ e q u ~
shearing time, t
inelastic, vi scous response
shearing time, t
Fig. 5. Different ki nds of t hi xot ropi c behavi our on st art up of shear aft er vari ous degrees of rest (neglecting
i nst rument inertia).
4. Viscoelasticity and thixotropy
Viscoelastic systems sheared in their linear region show t i me-dependency because the mi-
crost ruct ure 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 cont i nuousl y, i.e., it can flow, showing viscous effects.
Thus, when observed over all time (and frequency) scales, the system is viscoelastic.
For non-l i near vi scoel ast i c- - or simply inelastic but shear-thinning s ys t ems - - not only does
the mi crost ruct ure t ake 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
t hi xot r opy- - t hat while bot h 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-l i near region
where the structure is broken down by deformat i on as well as respondi ng to it.
Shear t hi nni ng can occur for many reasons, e.g.,:
al i gnment of rod-like particles in the flow direction;
loss of j unct i ons in pol ymer solutions;
rearrangement of mi crost ruct ure in suspension and emulsion flow and
breakdown of flocs.
Since changes in any of these states t ake some time to come about (either from rest or from
some ot her configuration), t hi xot ropy is always (in principle) to be expected from any shear-
t hi nni ng mechanism. However t hi xot ropy becomes significant when the time-scale over which it
is seen becomes significantly longer t han the response times of instruments used to measure
rheology or longer t han some flow time in a process, e.g., the average time a liquid takes to flow
t hrough a pipe. Thixotropic timescales can be longer t han viscoelastic timescales and are
practically i mport ant 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
nat ure of most mi crost ruct ural features which produce thixotropic effects (see above), it is
obvious t hat 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 concurrent l y a
breakdown/ rebui l di ng of bot h viscous and elastic responses.
H.A. Barnes / J. Non-Newtonian Fluid Mech. 70 (1997) 1-33 13
The picture presented becomes even mor e compl i cat ed when we consider the linear viscoelas-
tic response of a rebuilding structure, where the typical storage and loss mo d u l i - - G' and
G"- - cur ves evolve with time. This can be used as a measure of the rebuilding mode since the
test is conduct ed at l ow-enough stresses/deformations t hat the evolving structure is unaffected
by the deformat i on. The growt h of G' particularly is very sensitive to structure rebuilding. Barut
et al. [35] studied an acrylic pol ymer 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 rheomet er
at 200 Pa for 2 mi n and after this ceased, the linear oscillatory properties were moni t or ed for
10 min at strains less t han 0.1 over a frequency range 0. 03-62. 8 rad s 1. The form of the
rebuilding curve of the storage modul us was of a stretched exponential form:
G' = Gk - ( G" - G;)exp( - ktP). (4)
Williams and Ren [36] used the Virtual Gap Rheomet er operat i ng over the range 250-800 Hz
to examine the rebuilding of 0.045 g ml - 1 aqueous Laponi t e 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 t hat restructuring was significant over the
first 10 mi n 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 t hrough a power-l aw region, eventually (as it
must) flattening out at times greater t han 20 min.
Bouda and Mikegovfi [37] simultaneously moni t ored the AC conduct i vi t y and the storage
modul us G' to establish the bui l dup of a carbon black net work in a polyethylene melt. After an
initiation period where the conductivity was constant, it t hen increased rapidly. The time a 7.4
weight % sample t ook to show the rapi d increase was nearly 200 rain. Similar behavi our was
also observed for G'. They explained the observations as resulting from the setting up of a
cont i nuous net work, and using percolation t heory showed t hat the observed behavi our was
explainable on the basis of diffusion-limited aggregation of small clusters of pri mary carbon-
black particles under the action of Browni an mot i on. As the flocs collide and stick t oget her they
eventually form an i nt erconnect i ng net work as the percolation t hreshol d is reached, at which
poi nt bot h the electrical conductivity and the storage modul us G' rose rapidly, see also [38].
On the ot her hand, Greener and Connelly [39] poi nt out how easy it is to misinterpret
thixotropic loops, particularly if there is viscoelasticity present in the sample being tested. They
compar e the supposed thixotropic behavi our of an aqueous pol yacryl ami de solution with the
predicted behavi our of the Wagner model and show t hat all the effects are account ed for by the
non-l i near viscoelastic behavi our, and not by true thixotropy!
5. Typical thixotropic experiments
5.1. Thi x ot r opi c / hys t er es i s l oops
One of the favourite ways of measuri ng t hi xot ropy is to perform a l oop test; t hat is to say,
to linearly increase the shear rate (or sometimes shear stress) from zero to a maxi mum value,
and t hen to ret urn at the same rate to zero. This test coul d t hen be repeated again and again,
until eventually, a const ant l oop behavi our is seen, see Fig. 6. The area bet ween t he up and
down curve is aut omat i cal l y measur ed in some comput er - based r heomet er s as a measure of
t hi xot ropy.
Thi s ki nd of test is to be depreci at ed, for al t hough useful as a qui ck, qual i t at i ve pr ocedur e it
has a number of bad poi nt s. First, t he l oop test is oft en carri ed out t oo quickly, and inertia
effects due to t he measur i ng head are i nt r oduced but not always recognised. (However, inertial
effects can now be account ed for by some r heomet er soft ware packages. ) Secondl y, a test where
bot h shear rate and t i me are changed si mul t aneousl y, on a mat eri al where t he response is itself
a f unct i on of bot h shear rate and t i me - - a s t hi xot r opy obvi ousl y i s - - i s bad experi ment at i on,
because t he response cannot t hen be resolved i nt o t he separat e effects arising f r om bot h
variables. However t he pr obl em in i nt erpret i ng t he l oop is even mor e difficult when we realise
t hat t he first par t of t he behavi our on st art -up is essentially elastic. As t he strain becomes large,
this moves to non-l i near elastic response. I f t he behavi our were j ust linear elasticity, t hen t he
strain in a simple l oop test increases parabolically, and t he curve is concave t o start with, but
soon t ur ns over. At t he same t i me t he viscous behavi our can become appar ent in t he first
t endency to flatten out. The viscous behavi our t hen itself becomes nonl i near as t he st ruct ure
begins to break down at large strains. As t he strain rate increases furt her, t he liquid woul d like
to shear-t hi n, but this t akes t i me since t he st ruct ure cannot adj ust itself fast enough to r espond
to t he i ncreasi ng shear rate. When t he t i me is l ong enough and t he st ruct ure has br oken down,
t he down curve will be under t he up curve. Rebui l di ng will t hen begin to t ake place slowly. Even
wi t h an appar at us t hat r esponds perfectly to t he stress and strain, i nt erpret i ng t he dat a to obt ai n
t he par amet er s cor r espondi ng to a model is very difficult if not impossible.
A si mpl er and mor e sensible test for a t hi xot ropi c liquid is per f or mi ng and deri vi ng results
f r om step-wise experi ment s where t he shear rate or stress is changed f r om one const ant value to
anot her wi t h a carefully cont r ol l ed prehi st ory. Even so, it is i mpossi bl e to el i mi nat e an elastic
response and i nst r ument inertia.
5.2. Start-up experiments
Any experi ment t hat starts f r om rest is anot her ki nd of t hi xot r opi c test. The typical behavi our
of strain- or st ress-cont rol l ed experi ment s is shown in Fig. 7. Most , if not all, t hi xot ropi c
. . . . . . . . . . second loop
n'th loop
shear rate, 1/s
Fi g. 6. A t ypi cal t hi xot r opi c- l oop test.
H.A. Barnes /J. Non-Newtonian Fluid Mech. 70 (1997) 1-33 15
time of shearing
Fig. 7. Various flow regimes after start up.
mat eri al s t hat have been at rest for some t i me show viscoelastic behavi our , so t he i mmedi at e
response in such tests is elastic, t hen dependi ng on t he condi t i ons, a t hi xot r opi c response will be
seen ei t her as an over shoot in t he stress in st rai n-cont rol l ed experi ment s or an increase in t he
slope of t he st rai n-t i me curve in creep tests. Thi s somet i mes happens after a critical st rai n has
been achieved. Thi s initial elastic response giving way to a t hi xot r opi c viscous response makes
t he behavi our qui t e compl i cat ed.
5.3. Artifacts involved in measuring thixotropy
The greatest difficulty in under st andi ng and model l i ng t hi xot r opi c mat eri al s is knowi ng t he
effect of t h e - - o f t e n u n k n o wn - - d e f o r ma t i o n prehi st ory on t he liquid of interest. Thi s is
part i cul arl y t rue in si t uat i ons where a t hi xot r opi c liquid is subject t o mi xi ng and pumpi ng, or
even t he seemi ngl y simple t ask of filling a vi scomet er or rheomet er. I n bot h cases it woul d be
i nt erest i ng to be able t o predi ct t he subsequent flow even if onl y t he initial response was known,
say t he initial t or que on a vi scomet er oper at i ng at a cert ai n shear rate, or t he t or que on a mi xi ng
vessel pr i or t o t he l i qui d being pumpe d out.
A number of met hods have been devised t o establish a consi st ent initial condi t i on: fixed rest
t i me after sampl e l oadi ng; pre-shear at a prescri bed shear rate for a prescri bed t i me fol l owed by
a set rest peri od; pre-sheari ng to equi l i bri um at a low shear rate fol l owed by t est i ng at a hi gher
shear rate, etc. These el i mi nat e t he pr obl em in charact eri sat i on, but t hey can never compl et el y
el i mi nat e t he pr obl em in practise, since t he effects of prehi st ory on a previ ousl y unt est ed sampl e
is always unknown.
The mechani cal inertia of t he r ot at i ng member s in vi scomet ers and r heomet er s means t hat in
experi ment s where t he shear rate or stress is changed qui ckl y or i nst ant aneousl y, t he i nst r ument
response is delayed, and this is oft en mi st aken for t hi xot r opy, and, even if t hi xot r opy is present ,
it can compl i cat e its measur ement . Somet i mes t he presence of a low compl i ance spri ng
compl i cat es t he meas ur ement because t he out put of t he exper i ment relates t o t he spri ng wi ndi ng
up.
For t hi xot r opi c mat eri al s, as we have seen, a typical source of t he phe nome non is br eakdown
of flocs. However t he appear ance of appar ent slip at t he wall, e.g., depl et i on, can also arise f r om
flocs because t hey are large, see Barnes [41]. Thi s is a case where observi ng t he pressure gradi ent
alone will not differentiate or account for bot h effects. A detailed investigation of the internal
flow profile will alone show what is happening. As well as pipe flows, there are many apparent l y
simple flows where the shear rate or shear stress is not const ant 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 mi xers
Edwards et al. [40] found t hat the behavi our of a range of thixotropic materials in a series of
mixers was quite easy to characterise if one assumed t hat the mixer behaved in the same way as
a viscometer runni ng at the same shear rate as the average shear rate in the mixer. They used
an average shear rat e for the flow in a cylindrical vessel with anchor, helical ri bbon and helical
screw impellers, given by the impeller rot at i onal speed N (rev s - l) times a const ant dependi ng
on the impeller geometry, k, where values of k ranged from about 12 for the helical screws,
ar ound 20 for the anchor to 30 for the helical ribbon. They compar ed the t orque produced in
the mixer with the signal from a viscometer runni ng at the same shear rate, bot h of whi ch coul d
halve over the course of the experiment. For salad cream, t omat o ket chup, yoghurt , pai nt and
3 and 4% aqueous Laponi t e dispersions, they f ound t hat the average viscosity measured as a
funct i on of time in the mixer at a given impeller speed compar ed well with t hat from a
viscometer runni ng at the same shear rate. For the salad cream, t omat o ket chup, yoghurt and
paint, the viscosities agreed to within 10%. The predicted values for 3 and 4% Laponi t e agreed
reasonabl y well for the anchor and helical ribbon, but were between 20 and 40% too low for the
helical screws. This latter fact was probabl y due to the very non- Newt oni an and thixotropic
nat ure of the Laponi t e 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 devel opment 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,
al t hough a pump coul d cope with sheared material, it mi ght be unabl e to initiate flow of
material t hat has been at rest for some time. Cavi t at i on in the liquid within the pump can t hen
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 t han the fluid flowing at the
middle of the pipe. This results in a very fast and prol onged br eakdown near the wall, giving a
low viscosity layer t hat effectively lubricates the inner, more-viscous layers. I f the pipe is long
enough, the flow profile will evolve such t hat eventually the steady state profile is established.
However, for short pipes, characterising the flow can be quite complicated, with a non-l i near
H.A. Barnes /J. Non-Newtonian Fluid Mech. 70 (1997) 1-33 17
pressure profile down the pipe being a distinct possibility. Distinguishing t hi xot ropy from a
developing slip layer caused by particle depletion can be very difficult (see Barnes [41]).
Simple approaches have been made to analyze this probl em mathematically, see Godfrey' s
summary [4], but the ones wort h ment i oni ng are due to Kembl owski and Petera [42] and Cheng
and co-workers [43]. The kinds of i mport ant situations analyzed include start-up of fully
structured thixotropic fluids and then steady-state flow, in bot h cases with either a constant flow
rate or a given pressure drop. The analysis was complex and required extensive numerical
comput at i on.
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 unreport ed
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 t hem 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 t aken for rebuilding to
occur can cause the material to drain. This is obviously undesirable. The thixotropic breakdown
of paints is i mport ant when such paints are being put ont o the brush or brushed out. The
desirable properties of non-dri p 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)
Thi xot ropy 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 t apped in a glass container. Clays such as the natural Bentonites
and the manufact ured 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, wi t hout giving unwant ed viscoelastic effects found with some kinds of polymeric
18
Table 1
Paints, inks and coatings
H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33
Author(s) Ref. Details
Overdiep
Kuwano et al.
Iizuka and Na-
ganuma
Cornelius
Galli
Kutik
Kerle
Pila
Papo and Sturzi
Parmentier
Dubyaga et al.
Alessandrini
Walton
Craw ford
Staus and Edser
Berry
Iizuka and Na-
ganuma
Kobs and Voigt
Tsuritani
Toussaint
[44] Effect of thixotropy on film formation
[45] Thixotropy in automobile paints
[46] Review of thixotropes for paints
[47] Thixotropy in urethane modified alkyd resins
[48] Fumed and precipitated silica, and clays as thixotropes for plastic coatings
[49] Amorphous silica gel as thixotropes
[50] Thixotropy in polyester-based thixotropic resins
[51] Thixotropes for vinyl resin thick layer systems
[52] Bentone as a thixotrope for oxidised bitumen protective coatings
[53] Hydrogenated castor oil as thixotrope for wood treatment coating
[54] Effect of thixotropy on film properties of polyether polyurethanes
[55] Montmorillonite thixoptrope in oxidised bitumen paint
[56] Production of thixotropic paints
[57] Review of advantages of thixotropy for all coatings
[58] Thixotropic vinyl-based polymer household emulsion paint
[59] Thixotropic alkyd-resin and polyamide-based household paints
[60] Thixotropes for high-solids coatings
[61] Effect of thixotropy on thick film screen printing
[62] Thixotropy of printing suspension and paste inks
[63] Thixotropy in organic coatings
t hi ckener s. Howe ve r becaus e o f t he size o f t he cl ay pl at es t he r at e o f s t r uc t ur i ng is ver y sl ow a nd
al so t he di f f er ence bet ween t he f ul l y f o r me d s t r uct ur e at rest a nd t he f l owi ng di s per s i on is ver y
l arge.
7.4. Thixotropic oils and lubricants (see Table 4)
Gr eas es are t hi xot r opi c becaus e o f t he f l occul at i on o f t he di s per s ed mat er i al s us pe nde d i n t he
oil phase. Thi s is ver y i mp o r t a n t i n l ubr i cat i ng s i t uat i ons wher e t he gr ease has t o br e a k d o wn
on s hear i ng so t ha t no u n wa n t e d ext r a dr a g is exper i enced i n bear i ngs.
Table 2
Detergent systems
Wolff [64]
Rounds [65]
Moreno et al. [66]
Moreno et al. [67]
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
Tabl e 3
Clay suspensions
Ari pov
Legrand and
Cost a
Har et and Zarea
Shevchuk and
Shishkevich
Or azmur adov et
al.
Ryabchenko and
Agabal ' yant s
Schulz
Egashira
Rosenqvist
Nakai shi and Y a-
sutomi
Bendukidze et al.
Txoperena
[68] Thi xot ropy of mont mori l l oni t e dispersions
[69] Effect of shearing on thixotropic bentonite muds
[70] Effect of vibrations, electrolytes and t emperat ure on t hi xot ropy of clays
[71] Effect of oil-water emulsions on t hi xot ropy of mont mori l l oni t e-based muds
[72] Effect of electrolyte and various colloids on t hi xot ropy of bentonite clay suspensions
[73] Orientation-thixotropic effect in aqueous dispersions of mont mori l l oni t e clays
[74] Review of modified Bentonite (organoclay) organophilic thixotropes for coatings
[75] Effect of colloid chemistry on t hi xot ropy of clays
[76] Thi xot ropy in quick clay
[77] Effect of time scale of measurement on flow of clay suspensions
[78] Effect of Bentonite on storage properties of chlorinated rubber enamels
[79] Thi xot ropy in coatings for wood paints and varnishes
7.5. Thi xot ropi c coal suspensions (see Table 5)
Coal-oil and coal -wat er suspensi ons show consi derabl e t hi xot ropy, and pr obl ems
wi t h start up of pumps after st oppi ng t he flow can cause probl ems. The pump
dut i es requi red for flow of sheared suspensi ons are very di fferent f r om start up of a
rest ed suspensi on. Thi s can result in pump failure, since st art up t orques can be very
high.
Tabl e 4
Oils and lubricants
Wislicki [80] Thi xot ropi c properties ester-based synthetic lubricating oils
Czarny [81] Thi xot ropy in lithium and calcium-based greases
Szilas [82] Thi xot ropy in crude oils flowing in pipelines
20
Table 5
Coal suspensions
H. A. Barnes / J . Non-Newtonian Fluid Mech. 70 (1997) 1- 33
Usui [83]
De Jong [84]
Chakr abor t y [85]
Sabadell et al. [86]
Thi xot ropy and physical stability of coal slurries
Thi xot ropy of coal-water mixtures
Thi xot ropi c coal-water suspensions
Thi xot ropy of coal-oil suspensions
Table 6
Metal slushes
Erz
Vives et al.
Flemings et al.
Mada and
Ajersch
[87] Thi xocas t i ng- - a casting process for near-net -shape manufact ure al umi ni um alloys
[88] Thi xot ropy of t wo-phase metallic slurries
[89] Review of thixo-casting
[90] Thi xot ropi c of semi-solid al umi num-6% silicon carbide alloy reinforced with silicon car-
bide particles
7.6. Thixotropic met al 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 mi ght show
some thixotropy, the title is probably a mi snomer because shear t hi nni ng is perhaps even more
i mport ant t han 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 net work t hroughout the rubber solution. The rubber
solution itself is shear thinning, and the carbon black net work also renders a degree of shear
thinning, but it is also thixotropic.
Table 7
Rubber systems
Gent and [91]
Al an
Lomov et al. [92]
Kat i shonok et [93]
al.
White [94]
Thi xot ropy in rubbers containing particulate fillers
Thi xot ropy of nitrile rubber system with combi ned steady-state flow and vi brat i on
Thi xot ropi c for solutions of chlorinated rubber
Review of t hi xot ropy in carbon-bl ack rubbers
H.A. Barnes/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33
Table 8
Food and biological systems
21
Author(s) Ref . Details
Benezech and Main- [ 95] Thixotropy in set, stirred and drinking yoghurts
gonnat
Noik et al. [96]
Battistoni et al. [97]
Morris et al. [98]
Baxter [99]
Divjak [100]
Thixotropy of xanthan protein complexes obtained by fermentation
Thixotropy of digested municipal solid-wastes
Thixotropy of acetan and related xanthan gum polysaccharide solutions
Thixotropy of sludge in anaerobic digestors
Thixotropy in xanathan-gum-based low-calorie mayonnaises and salad dressings
7.8. Thixotropic f o o d and biological syst ems (see Table 8)
Ma n y f ood and bi ol ogi cal syst ems ar e well known exampl es of t hi xot r opy. For i nst ance,
st i rri ng yoghur t s makes t hem t hi nner , but l eavi ng t hem t o rest t her eaf t er t hi ckens t hem agai n.
Thi xot r opy in f ood t hi ckener s such as xant han gums can cause pr obl ems in t hat t he suspendi ng
pr oper t i es t hey give t o liquids ma y t ake t i me t o appear aft er shear i ng and this coul d cause some
initial sedi ment at i on or cr eami ng of suspended mat eri al .
7.9. Thixotropic creams and pharmaceuticals product s (see Table 9)
Cr eams and ot her per s onal - pr oduct and phar maceut i cal mat er i al s ar e gi ven ' body' by usi ng
ma t e r i a l s - - s o- c a l l e d t h i x o t r o p e s - - t h a t happen t o be t hi xot ropi c. Her e t he ori gi nal meani ng of
t hi xot r opy as conf er r i ng gel-like pr oper t i es is still ver y of t en t he cont r ol l i ng idea. The t i me
effects seen in usi ng t hese mat er i al s are t her ef or e agai n onl y of nui sance val ue.
7.10. Other thixotropic suspensions (see Table 10)
Some ot her exampl es ar e ci t ed wher e t hi xot r opy is seen in st r uct ur ed liquids of di f f er ent
ki nds, mos t of whi ch are f l occul at ed in some way, r angi ng f r om fl occul at i on i nduced by
decr easi ng dr opl et size in emul si ons t hr ough t o t he del i berat e addi t i on of t hi xot r opes.
Table 9
Creams and pharmaceuticals
Okor [101]
Junginger [102]
Matsumoto and Nakata [103]
Assmus [104]
Y amamura [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
Ueda
Faitel'son
Nemets et al.
Shul'man et
al.
Veliev and
Abdinov
Stepita
Ito
Gao et al.
Arima and
Eguchi
Kruger and
Hulsenberg
Fedotova
Sakka and
Kozuka
Tretinnik
[106] Thixotropy in fine emulsions produced using a high-pressure homogenizer
[107] Thixotropic properties of epoxy resin polymers
[108] Thixotropy in aluminum and zirconium oxides suspensions
[109] Thixotropy of electrorheological suspensions
[110] Thixotropy in magnetically active (ferromagnetic dust) liquids
[111] Alkali metal silicates and montmorillonite as thixotropes in limestone-based plaster
[112] Thixotropy in silica(Aerosil)-based adhesives
[113] Thixotropes (silicas, calcium carbonate or PVC) in unsaturated polyester resin
[114] Aerosil as a thixotrope
[115] Effect of electrolyte on thixotropy in ceramic slips
[116] Effect of additives on aqueous poly(vinyl alcohol) thixotropy
[117] Development of thixotropy in metal alkoxide solutions undergoing hydrolysis and con-
densation reactions.
[118] Thixotropic in silicate suspensions
7.11. Mo r e e x a mp l e s in det ai l
It is i nt er est i ng t o select a gr oup of r ecent paper s t o s t udy t hei r di f f er ent appr oaches . Ra ms a y
a nd Li nder [119] st udi ed mont mor i l l oni t e c l a y - - a nat ur al l y occur r i ng cl ay f r om Cr o o k Count y,
Wy o mi n g USA. The size of t hese cl ay pl at es is cons i der abl y bi gger t ha n La poni t e and t hei r
shape is less well defi ned. Us i ng smal l - angl e ne ut r on scat t er i ng ( SANS) , t hey s howed t hat unde r
shear, t he s hor t - r ange i nt er act i ons di s appear ed. The y s howed t hat t he ani s ot r opi c st r uct ur e
br ought a bout by shear i ng r e ma i ne d f or ma n y hour s , even days, aft er t he shear was r emoved.
Thi s was in accor d wi t h t hei r G' meas ur ement s . Thes e s howed t hat t he s t r uct ur e bui l t up qui ckl y
whi l e t he part i cl es were still al i gned. It t ook a l ong t i me bef or e c ompl e t e i s ot r opy was achi eved.
They suggest t ha t mont mor i l l oni t e is well descr i bed by t hi s expl anat i on, but t he br e a kup of flocs
is a mor e l i kel y expl anat i on in La poni t e wi t h its smal l er pl at es. Thus , t he mont mor i l l oni t e
sampl es are mor e t hi xot r opi c. The r ebui l di ng is dr i ven by Br owni a n forces whi ch t ake l onger t o
al i gn l ar ger part i cl es l i ke mont mor i l l oni t e . They al so not e i n passi ng t hat t he l i near el ast i c l i mi t
moves t o hi gher shear.
Z ha ng a nd Nguye n [120] used a t echni que t o meas ur e t he r ebui l di ng of t he yi el d stress for
ma yonna i s e t hat rel i ed on t he pos i t i on of a ppa r e nt cessat i on of fl ow in a wi de- gap concent r i c
cyl i nder appar at us . Up t o 1000 s was needed bef or e t he yi el d-l i ne came t o a c ons t a nt posi t i on.
Takeeshi , Wei and Sat o [121] s t udi ed t he t hi xot r opi c r esponse of f ume d silicas (Aerosi l 200
and OX 50) s us pended in pol ybut adi ent es of var i ous vi scosi t i es (1, 11, 33 Pa s). Af t er shear i ng,
t he nor ma l ne t wor k st r uct ur e r ebui l ds slowly, wi t h cons i der abl e di fferences still occur r i ng at 8
h, but i nt er est i ngl y if a 15% st rai n was i mpos e d f or even 2 mi n, t he st r uct ur e became st i ffer still
f r om rest. Thi s is an exampl e of a s hear - enhanced f l occul at i on i f t he shear is l i mi t ed.
Bret on-Dol l et et al. [122] measured the thixotropic behavi our of maize starch pastes using a
loop-test met hod, not i ng the area under the curve as a measure of thixotropy. It remai ned fairly
const ant as a funct i on of t emperat ure for the first loop for maize, but was lower and thereafter
decreased significantly as a funct i on of t emperat ure for the second and t hi rd loops. Unfort u-
nately in this case, no at t empt seems to have been made to establish any equilibrium dat a. For
waxy starch pastes, the t hi xot ropy was lower and a decreasing function of t emperat ure and the
number of loops. The difference in behavi our was at t ri but ed to the presence of amylose and
amyl opect i n in the maize starch.
Berland and Launay [123] exami ned the thixotropic behavi our of wheat flour doughs and
showed t hat thixotropic effects are seen in flows ot her t han steady shear. They measured the
thixotropic recovery of the storage modul us measured in the linear region (0.2% strain) after
straining at higher strain amplitudes in the nonl i near region. Recovery is compl et e- - al t hough
t aki ng many mi nut e s - - up to large ampl i t ude stains of ar ound 20%. Above that value,
irreversible changes seemed to occur.
7.12. Bl ood
Thi xot ropy in bl ood has been recognised for a long time, but a maj or probl em encount ered
in investigating restructuring of individual bl ood cells into aggregates called roul eau is t hat
sedi ment at i on takes place quite quickly as the aggregates form. Hence the full potential of
restructuring is not always seen. Of course the circulation takes bl ood t hr ough many flow
regimes, and the br eakdown and recovery of structure is i mport ant especially in bl ood sensitive
to aggregation. A general review on the experimental wor k on human bl ood viscoelasticity and
t hi xot ropy was presented by Stoltz and Lucius [124], who showed t hat some models used for
pol ymer solutions coul d also be used to account for the phenomena observed with bl ood
(transient and periodic flow). Being more specific, Huang et al. [125] studied the effect of
haemat ocri t (red cell concent rat i on) on thixotropic parameters. They f ound t hat the rat e
const ant of t hi xot r opy- - i n this case arising from the br eakdown of roul euax into individual red
cel l s- - was i ndependent of the haematocrit.
8. Mathematical theories
8.1. Requi rement s o f usef ul model s
The ideal model to describe thixotropic behavi our woul d start from the fact t hat some
fundament al , rheol ogy-det ermi ni ng physical entity takes time to change when the flow field
ar ound it has changed or is changing. As we have already said, this mi ght be for example the
size of a floc; the ori ent at i on angle of an alignable particle or the density of transient
entanglements. In the simplest models, all such fundament al paramet ers change instantly with,
for instance, shear, shear rate or shear stress. First we have to know at what rate these changes
t ake place, and t hen if we know how the mi crost ruct ure 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 at t empt ed to describe viscoelastic effects. Representative
examples of classes of theories are described below and others in t hat field are noted.
8.2. Viscous theories
Current theories for t hi xot ropy fall i nt o three groups: first those t hat use a very general
description of mi crost ruct ure described by a numeri cal value of a scalar paramet er, typically 2,
and then use d2/ dt as the worki ng parameter; second those who at t empt some direct description
of the t emporal change of mi crost ruct ure as for instance, the number of bonds, or an at t empt
at describing real floc architecture using fractal analysis, and t hi rd those t hat use the viscosity-
time dat a itself on whi ch to base a theory.
8.2.1. Indirect microstructural theories
Most workers in this area have developed mat hemat i cal theories of t hi xot ropy based on the
numeri cal scalar measure of structure, often designated by 2. Using this simplistic cypher,
completely built structure is represented by 2 = 1 and completely br oken- down structure as
2 = 0. In the simplest case of a typical, inelastic, non- Newt oni an liquid with upper and lower
Newt oni an viscosity plateaus, 2 = 1 corresponds to t/o and 2 = 0 corresponds to t/a, with points
between t aki ng intermediate values.
Then t hi xot ropy is usually i nt roduced via the time derivative of the structure paramet er,
d2/ dt , whi ch is given by the sum of the bui l dup and br eakdown terms, which, in the simplest
theories, are only cont rol l ed by the shear rate and the current level of structure 2. The most
general description of the rate of br eakdown due to shearing is given by the pr oduct of the
current level of structure and the shear rate raised to some power, and the driving force for
bui l dup as cont rol l ed by the distance the structure is from its maxi mum value, i.e., ( 1 - 2),
raised to anot her power. Then
d2
= g(~, 2) = a(1 - 2) h - c2~ d, (5)
where a, b, c and d are constants for any one system. I f the value of g(~, 2) is negative, the
system is breaki ng down t owards equilibrium; if it is positive, it is building up t owards
equilibrium. At equilibrium, for every value of ~ there is a part i cul ar value of 2 whi ch in this
equat i on is f ound by setting d,~/dt to zero.
Godfrey [4] has summari sed the devel opment of these two-process models beginning with
Goodeve and Whitfield in 1938 [126] which led to an earlier version of the above equat i on due
to Moor e [127] with bot h b and d as unity, and progressing t hr ough Cheng and Evans [128] who
made b unity, but allowed d to be non-uni t ary, t hr ough to the very general ' structural kinetics'
model of Mewis, with bot h powers t aki ng non-uni t ary values. This latter formul at i on was also
used by Lapasi n' s group [129]. The next step in this ki nd of approach is to relate the structure
2 - - a s calculated using the equat i ons a bove - - 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
Bi ngham equation, t hrough the Cross model to a Cross-like model cont ai ni ng a yield stress.
Most of the differences between the theories in this area are account ed for in the various
combi nat i ons of these structure change and structure-viscosity formulations.
Baravian, Q uemada and Parker [130] recently proposed a modification of the Cheng and
Evans approach. Thei r study is wor t h l ooki ng at in detail for two reasons. First it follows the
t radi t i on rout e to describing thixotropy, and second, it shows how long and seemingly involved
the procedure to describe t hi xot ropy becomes.
They postulate t hat the relationship between viscosity and structure is given by
q(0-, t) = q(2) = (1 K2)2 , K= 1 - (6)
- \ r i o /
where % and ~/~ are the usual limiting values of viscosity at very low and very high shear
rate/stress, respectively. This assumes t hat the effect of stress on the viscosity is also account ed
for within the current value of the structural paramet er 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 convert ed into values of R. They
found t hat the relationship between the equilibrium value of the structural paramet er 2 and the
shear stress 0- was given by
Requit(0- ) ~ - - - [1 - I - ( 0 - / 0 - c ) p ] --1 (8)
Fr om any one part i cul ar equilibrium position of stress, 1 Pa j umps 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 obt ai ned for many values of equilibrium stress. The values of the
const ant s were t hen described by the equation:
R(t) = Requi~ + (2i ni - 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 funct i on of stress. This t heory was
able to describe a l oop test very well, once i nst rument inertia had been account ed for.
Ot her variations on this t heme include t hat of De Kee et al. [131], (following Tiu and Boger
[132]), who described the break-down behavi our of various food systems by
dR
- - c ~ ' d ( R - - Requil) n. (1 1)
dt
The viscosity was described by a multiple exponential-type flow law
0(9) = R(0-o + 9Zr/i,e- 'P~). (12)
The t heory was used to characterise viscosity decay curves for yogurt and mayonnai se.
8.2.2. Di rect st ruct ure theories
Denny and Brodkey' s applied reaction kinetics to t hi xot ropy via a simple scheme t hat l ooked
at the distribution of broken and unbr oken bonds [133]. The number of these bonds was later
linked to viscosity. The forward and reverse rate const ant s k'~ and k2 represented the br eakdown
kinetics in flow, and the bui l dup 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 br eakdown as (cp. Ruckenst ei n and Mewis [135]):
26 H. A. B a r n e s / J . Non- Ne wt oni an Fl ui d Mech. 70 (1997) 1 - 3 3
d(unbroken)
- kl (unbroken) n - k 2 ( b r o k e n ) m, (13)
dt
and solved to give the viscosity by assuming it is linearly proport i onal to the amount of
unbr oken structure, with a maxi mum value when completely structured of r/o and a mi ni mum
value when completely dest ruct ured of r/~. The rate const ant k2 is assumed to be i ndependent
of shear rate, being merely a description of Browni an collisions leading to restructuring, while
the rate of br eakdown const ant is related to shear rate by a power-l aw expression.
The way the wel l -known Cross model was derived is instructive [136]. Assumi ng t hat a
structured liquid was made up of flocs of r andoml y linked chains of particles, Cross derived a
rate of equat i on of the form:
dN
= k 2 P - (ko + kl ~) m) N, (14)
d t
where N was the average number of links per chain, k2 was a rate const ant describing Browni an
collision, ko and kl were rate const ant s for the Browni an and shear cont ri but i ons to break-
down, P was the number of single particles per unit volume, and m was a const ant less t han
unity. At equilibrium d N / d t is zero, so
k 2 P
N~= ( k, ) " (15)
ko 1 +~o~) m
Then assuming t hat the viscosity was given by a constant, r/~ plus a viscous cont ri but i on
proport i onal to the number of bonds Are, he derived his wel l -known relationship:
F/e -- r/a, _ 1 (16)
- - k l " m
r/o r/~ 1 + ~ 7
Cross coul d of course have used the non-equi l i bri um dat a 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 comput er simulations based on the ballistic, cl ust er - cl ust er aggregation
mechani sm suggested t hat Cfp in Q uemada' s model, i.e., 2/[q]Om in the KD equat i on, is given by
B + A ( N ~+ x I - 1) ( 17 )
Cf p = B + Nmax - 1
where A and B are constants, Nmax is the number of pri mary particles in a floc, and fl is given
by 3 / D- 1, where D is the fractal di mensi on of the floc. Then Lapasi n et al. argue t hat (cf.
Cheng and Parker)
dNm,x
- - - a ( N - Nmax) - b~rP(Nmax - - Nmax~) (18)
dt
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
a N
Nmax = Nmax,~ + _~_o- 1, (19)
which, once we have replaced the l umped paramet er ( a N/ b ) L'p by a critical stress oc and
substituted into the Kri eger-Doughery equation, gives
q -(1/2) qb B + A Nm, ~x~ + a /s
- - = 1 ( 2 0 )
L r / ~ J ~bma x B A -N m ax,~ +(~--~-~ " - - 1
\o-,./
This equat i on describes the br eakdown of flocs under flow, and predicts a yield stress and a
finite high-shear-rate viscosity. It described very well the behavi our of bot h TiO2 and mica
dispersions in steady state. (A much more complicated t heory of this kind had been proposed
by Eyring much earlier [see [138]]).
8.2.3. Si mpl e vi scosi t y t heori es
Frederi ckson [139] formul at ed an expression for the rate of change of fluidity (the inverse
of viscosity) of a non- Newt oni an 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 Newt oni an plateaus at equilibrium, and if the quadrat i c dependence on shear-rate is
replaced by a power-l aw relationship, they become similar.
Mewis and Schryvers [28] have recently devised a t heory t hat also circumvents the use of any
structural paramet er such as 2, and instead used the viscosity as a direct measure of structure.
They proposed t hat the rate of change of viscosity rat her t han 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 (Newt oni an) assumption t hat r/e,0 = r/i,~ which makes the
use of the equat i on simpler since it is much easier to measure the eventual viscosity of the initial
steady state condition. This assumes t hat the viscosity at the end of the initial steady-state period
is the same as t hat at the beginning of the new shear-rate test, i.e., t hat the system is essentially
Newt oni an between those conditions. This is reasonable under some condi t i ons but as Mewis' s
previous work has shown, it is only strictly t rue for most systems at higher shear rates. Using
a value of n of 5/3, they fitted experimental dat a very well for carbon black in mi neral oil.
Kristensen et al. [140] model l ed the thixotropic br eakdown behavi our of maize starch pastes
using the equation:
28 H.A. Barnes,/J. Non-Newtonian Fluid Mech. 70 (1997) 1-33
( 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 dest ruct ured states, respectively) measured at time t any part i cul ar 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 t hat
the dat a was satisfactorily described by m = 3, thus suggesting a t hi rd-order kinetic model.
Over the shear rate range tested, the steady-state flow curves coul d be described by a
power-law model with an approxi mat e half-power.
8.3. Viscoelastic theories
Al most any viscoelastic t heory can have t hi xot ropy i nt roduced if the part i cul ar paramet ers
t hat give the viscous and elastic responses are made to change in the way we have described
for purely viscous behaviour. Probabl y the best example of this approach is given by the
model due to Aci erno et al., [142] who consi dered 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 t hat they coul d be represented by a cont i nuous spectrum. Simplifying the model to a
discrete series, it is possible to write down the behavi our as
a = Z,a,, ~ + O, d t \ O J = 0;i (25)
where a~ is the stress, G~ the modul us, and 0 the relaxation time ( = ~Ii/G~ and labelled 2g in
their paper) of the ith element in the discrete spectrum.
Thi xot ropy is i nt roduced via the well-used structure paramet er 2 (labelled as x; in their
paper):
G~ = Go,2;, 0~ = 00,2] '4 (26)
The rate equat i on is t hen given by
a , F E ,
(27)
dt 0i 0i L6;]
i / ~ /
where Ei is the i nst ant aneous elastic energy in the ith element. This is the same as the Moor e
linear model, except t hat now ~ is replaced by the generalised expression (E/Gi)~/2/Oi t hat
account s for the elasticity as well as the viscosity. The t heory gives an excellent description
of most of the rheological behavi our of a low-density polyethylene melt in shear and exten-
sional transient and steady-state flow. The model is equivalent to the Moor e model if
reduced to the viscous case. Shoong and Shen [143] i nt roduced a power-l aw dependence of
the br eakdown t erm which t hen compares with the Cheng and Evans' inelastic model. An
obvious extension is to raise bot h terms to non-uni t ary powers.
9. The breakdown and build- up of isolated flocs
The two key mechani sms of t hi xot ropy for typical systems are floc erosion and Browni an
collisions. Wor k has been published on these topics for diluted flocs and it is instructive to relate
these studies to thixotropic bui l d-up and br eakdown of suspensions of flocs.
The diffusion rate of isolated flocs decreases significantly as their size grows. Reynol ds and
Goodwi n [144] measured the diffusion coefficients of isolated flocs and f ound a rapid decrease
of diffusion rate with floc size, with the particular value dependi ng on the floc geomet ry which
they studied as linear or clustered flocs. As these are quite moderat e floc sizes, it is obvious t hat
very large flocs of hundreds or t housands of pri mary particles will move very sluggishly. The
effect of pri mary particle size on translational diffusion coefficient was worked out by Einstein
who showed a simple inverse dependence on size. However the rot at i onal diffusion of particles
scales as the inverse cube of particle size (see [145]). This behavi our explains why exponential-
type expressions for rebuilding cont ai n a driving force such as (1 - 2), because rebuilding starts
at a given floc size t hat grows and t hen the diffusion coefficient decreases. This means t hat
collisions become less frequent, and as rebuilding progresses it gets slower and slower, but
theoretically never stops.
The br eakdown of isolated flocs in imposed shear fields has been studied by a number of
workers. Sonnt ag [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 pri mary particles, t / t he viscosity of the cont i nuous phase and ~ is the
shear rate. It is this stress which produces surface erosion of pri mary particles if it is greater t han
some bond shear strength between the pri mary particles [see Mtihle [146]]. This expression shows
t hat floc br eakdown in a given shear field is fastest for the largest sized flocs, i.e., at the shortest
times, as well as being proport i onal to the shear rate raised to a power. These facts are reflected
in the structure br eakdown criteria normal l y used, d2/ dt Qc - 2 . ~ ",n.
I0 . O verall conclusions
Thi xot ropy comes about first because of the finite time t aken for any shear-induced change in
mi crost ruct ure to t ake place. The mi crost ruct ure is brought to a new equilibrium by compet i t i on
between the processes of tearing apart by stress and flow-induced collision, in a time t hat can be
minutes. Then, when the flow ceases, Browni an mot i on is able to move the elements of the
mi crost ruct ure ar ound slowly to more favourable positions and rebuild the structure. This can
t ake many hours to complete. The whole process is completely reversible.
The position of various areas of t hi xot ropy t oday is well summari sed by three quotations:
(1) As to the proper underst andi ng of the word itself, we can do no better t han quote from
Lewis Carrol l ' s Alice in Wonderl and, "When I use a wor d, " Humpt y Dumpt y said ... "it means
j ust what I choose it to me a n- - ne i t he r more nor less". "The question is", said Alice, "whet her
you can make so many words mean so many different things".
(2) As to the state of experimental investigation in thixotropy, we quot e Godfrey [4],
"Thi xot r opy is one of the more complex characteristics associated with the behavi our of
non- Newt oni an liquids ... most of the available [experimental] dat a leave somet hi ng to be
desired".
30 H. A. Bar nes / J. Non-Newtonian Fluid Mech. 70 (1997) 1- 33
(3) The n t o assess t he st at e o f pr ope r t heor et i cal u n d e r s t a n d i n g of t hi xot r opy, par t i cul ar l y i n
vi scoel ast i c syst ems, " Th e r esul t s obt a i ne d so f ar do not al l ow [sic] t o cons i der t he model l i ng o f
t he t hi xot r opi c vi scoel ast i c be ha vi our as a sol ved p r o b l e m" , La pa s i n a nd Pri cl [16], but see [147].
Thus , we concl ude t ha t t her e is pl ent y o f scope f or mor e wor k in t hese t hr ee areas; viz, a f ul l er
def i ni t i on, a bet t er col l ect i on o f d a t a on wel l - char act er i s ed mode l syst ems a n d t he n t he need f or
a c ompr e he ns i ve t h e o r y t ha t descr i bes b o t h vi scous a nd vi scoel ast i c t hi xot r opi c effect s: c ompu-
t a t i ona l ef f or t s s uch as mol e c ul a r mode l l i ng will be ver y i mp o r t a n t i n such st udi es because o f t he
l ar ge n u mb e r o f var i abl es t ha t woul d ensur e, as will t he i nt r oduc t i on of t hi xot r opy i nt o CF D
codes.
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ELS EVI ER J. Non-Newtonian Fluid Mech.

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