Non-Newtonian fluid behaviour 15

1.4Time-dependent fluid behaviour

The flow behaviour of many industrially important materials cannot be
described by a simple rheological equation like (1.12) or (1.13). In practice,
apparent viscosities may depend not only on the rate of shear but also on the
time for which the fluid has been subjected to shearing. For instance, when
materials such as bentonite-water suspensions, red mud suspensions (waste
stream from aluminium industry), crude oils and certain foodstuffs are sheared
at a constant rate following a long period of rest, their apparent viscosities
gradually become less as the ‘internal’ structure of the material is progressively
broken down. As the number of structural ‘linkages’ capable of being broken
down decreases, the rate of change of apparent viscosity with time drops
progressively to zero. Conversely, as the structure breaks down, the rate at
which linkages can re-form increases, so that eventually a state of
16 Non-Newtonian Flow in the Process Industries

dynamic equilibrium is reached when the rates of build-up and of break-down

are balanced.
Time-dependent fluid behaviour may be further sub-divided into two cate-
gories: thixotropy and rheopexy or negative thixotropy.

1.4.1 Thixotropy

A material is said to exhibit thixotropy if, when it is sheared at a constant

rate, its apparent viscosity (or the corresponding shear stress) decreases with
the time of shearing, as can be seen in Figure 1.10 for a red mud suspension
[Nguyen and Uhlherr, 1983]. If the flow curve is measured in a single experi-
ment in which the shear rate is steadily increased at a constant rate from zero
to some maximum value and then decreased at the same rate to zero again, a
hysteresis loop of the form shown in Figure 1.11 is obtained; the height, shape
and enclosed area of the hysteresis loop depend on the duration of shearing,
the rate of increase/decrease of shear rate and the past kinematic history of
the sample. No hysteresis loop is observed for time-independent fluids, that
is, the enclosed area of the loop is zero.
The term ‘false body’ has been introduced to describe the thixotropic
behaviour of viscoplastic materials. Although the thixotropy is associated
with the build-up of structure at rest and breakdown of structure under shear,
viscoplastic materials do not lose their solid-like properties completely and can
still exhibit a yield stress, though this is usually less than the original value
of the virgin sample which is regained (if at all) only after a long recovery
period.

Shear
rate (s−1)
30 56
Shear stress (Pa)

28

20 14

3.5
10

59% wt solids red mud

0
0 500 1000 1500 2000 2500
Time (s)

Figure 1.10 Representative data showing thixotropy in a 59% (by weight)

red mud suspension
 Non-Newtonian fluid behaviour 17

Thixotropic fluid
Shear stress

Rheopectic fluid

Shear rate

Figure 1.11 Schematic shear stress–shear rate behaviour for time-dependent

fluid behaviour

Other examples of materials exhibiting thixotropic behaviour include con-

centrated suspensions, emulsions, protein solutions and food stuffs, etc.
[Barnes, 1997].

1.4.2 Rheopexy or negative thixotropy

The relatively few fluids for which the apparent viscosity (or the corresponding
shear stress) increases with time of shearing are said to display rheopexy or
negative thixotropy. Again, hysteresis effects are observed in the flow curve,
but in this case it is inverted, as compared with a thixotropic material, as can
be seen in Figure 1.11.
In a rheopectic fluid the structure builds up by shear and breaks down
when the material is at rest. For instance, Freundlich and Juliusberger [1935],
using a 42% aqueous gypsum paste, found that, after shaking, this material re-
solidified in 40 min if at rest, but in only 20 s if the container was gently rolled
in the palms of hands. This indicates that gentle shearing motion (rolling)
facilitates structure buildup but more intense motion destroys it. Thus, there is a
critical amount of shear beyond which re-formation of structure is not induced
but breakdown occurs. It is not uncommon for the same dispersion to display
both thixotropy as well as rheopexy depending upon the shear rate and/or
 18 Non-Newtonian Flow in the Process Industries

the concentration of solids. Figure 1.12 shows the gradual onset of rheopexy
for a saturated polyester at 60° C [Steg and Katz, 1965]. Similar behaviour is
reported to occur with suspensions of ammonium oleate, colloidal suspensions
of a vanadium pentoxide at moderate shear rates [Tanner, 1988], coal-water
slurries [Keller and Keller Jr, 1990] and protein solutions [Pradipasena and
Rha, 1977].

−1
45 g = 8267 s

40

35

30
4133 s−1
Shear stress (kPa)

25

2755 s−1
20

15

1377 s−1
10
918.5 s−1

0
0 20 40 60 80 100 120 140
Time of shearing (min)

Figure 1.12 Onset of rheopexy in a saturated polyester [Steg and Katz,

1965]

It is not possible to put forward simple mathematical equations of general

validity to describe time-dependent fluid behaviour, and it is usually necessary
to make measurements over the range of conditions of interest. The conven-
tional shear stress–shear rate curves are of limited utility unless they relate
to the particular history of interest in the application. For example when the
material enters a pipe slowly and with a minimum of shearing, as from a
storage tank directly into the pipe, the shear stress–shear rate–time curve
should be based on tests performed on samples which have been stored under
 Non-Newtonian fluid behaviour 19

identical conditions and have not been subjected to shearing by transference

to another vessel for example. At the other extreme, when the material under-
goes vigorous agitation and shearing, as in passage through a pump, the shear
stress–shear rate curve should be obtained using highly sheared pre-mixed
material. Assuming then that reliable flow property data are available, the
zero shear and infinite shear flow curves can be used to form the bounds for
the design of a flow system. For a fixed pressure drop, the zero shear limit
(maximum apparent viscosity) will provide a lower bound and the infinite
shear conditions (minimum apparent viscosity) will provide the upper bound
on the flowrate. Conversely, for a fixed flowrate, the zero and infinite shear
data can be used to establish the maximum and minimum pressure drops or
pumping power.
For many industries (notably foodstuffs) the way in which the rheology of
the materials affects their processing is much less significant than the effects
that the process has on their rheology. Implicit here is the recognition of
the importance of the time-dependent properties of materials which can be
profoundly influenced by mechanical working on the one hand or by an aging
process during a prolonged shelf life on the other.
The above brief discussion of time-dependent fluid behaviour provides an
introduction to the topic, but Mewis [1979] and Barnes [1997] have given
detailed accounts of recent developments in the field. Govier and Aziz [1982],
moreover, have focused on the practical aspects of the flow of time-dependent
fluids in pipes.