The Flow Properties of Two Types of Non-Newtonian Fluid

Author(s): E. W. Billington
Source: Proceedings of the Royal Society of London. Series A, Mathematical and Physical
Sciences, Vol. 302, No. 1468 (Dec. 5, 1967), pp. 1-23
Published by: Royal Society
Stable URL: http://www.jstor.org/stable/2415884
Accessed: 30-10-2015 16:38 UTC

Your use of the JSTOR archive indicates your acceptance of the Terms & Conditions of Use, available at http://www.jstor.org/page/
info/about/policies/terms.jsp

JSTOR is a not-for-profit service that helps scholars, researchers, and students discover, use, and build upon a wide range of content
in a trusted digital archive. We use information technology and tools to increase productivity and facilitate new forms of scholarship.
For more information about JSTOR, please contact support@jstor.org.

Royal Society is collaborating with JSTOR to digitize, preserve and extend access to Proceedings of the Royal Society of
London. Series A, Mathematical and Physical Sciences.

http://www.jstor.org

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
Proc. Roy. Soc. A. 302, 1-23 (1967)
Printed in Great Britain

The flow properties of two types of non-Newtonian fluid

BY E. W. BMLINGTON
Royal ArmamentResearchand DevelopmentEstablishment,Fort Halstead, Kent

Goodeve,F.B.S.-Received 16 August 1966)

(Communicatedby Sir hcharles
The impulse theory of flow has been extended to include the rotational motion of the particles
of the minority component of certain types of suspension which exhibit non-Newtonian flow
behaviour. Some physical considerations are discussed for the flow of a suspension of identical
rigid spheres dispersed in a continuous medium exhibiting Newtonian flow behaviour.
Steady translational motion produces a steady state distribution of single spheres and multi-
particle aggregates, consisting of two or more spheres, which are generated by shear induced
collisions amongst the various species of particle. The present discussion is, however, limited
to an ideal system consisting of single spheres and aggregates containing only two individual
spheres, a multi-link bond being formed between colliding spheres. The two-particle aggre-
gates are approximated to rigid ellipsoids, the rotational and translational motion of the
aggregates and the associated hydrodynamic drag forces being considered in relation to the
particle-mobility approximation. By specifying the way in which the bond formed between
colliding spheres behaves under tension, an expression for the associated impulse has been
developed which in turn yields the rheological equation of state. Two regions of flow are
distinguished; with increasing flow rate the strength of the bond increases, ultimately reaching
saturation at a particular flow rate. For a saturated bond the rheological equation of state is
formally similar to that of an ideal Bingham plastic.
An experimental technique has been developed which involves measurement of the whole
of the transient flow behaviour of the fluids. The measurements yield the shear stress-rate
of flow characteristics corresponding to both the initial and final rheological states of the
fluids which exhibit thixotropic flow behaviour. Some experimental results are presented for
a non-thixotropic fluid and for two fluids which exhibit thixotropic flow behaviour, the
measurements being obtained with a coaxial cylinder viscometer. The rheological equations
of state, derived by way of the impulse theory of flow, correlate favourably the shear stress-
rate of flow measurements for all three fluids.

1. INTRODUCTION
Fluids which deviate from Newtonian type flow behaviour are considered anomalous,
two classes of non-Newtonian fluid being distinguished depending upon whether
the flow properties are time independent or vary with the time of shearing. The
individual elements of the internal structure of certain types of anomalous fluid can
be linked to produce a continuous structure throughout the bulk of the fluid, an
example being the continuous structure developed in certain dilute carbon suspen-
sions (McDowell & Usher I 93 i). Fluids of this type generally exhibit the behaviour
of a weak solid for small flow rates, the simplest example being the ideal Bingham
plastic. A general theory describing the flow properties of anomalous fluids, and in
particular those of an ideal Bingham plastic has been developed by Goodeve (1938,
I939 a, I949). It is assumed by Goodeve that communal hydrodynamic effects and
direct particle interaction effects involving rupture of bonds are simply additive,
and that during the process of interaction accompanied by rupture of bonds, an
impulse is transmitted from a fast moving layer to a slower adjacent layer of the
fluid. Measurements of the flow properties of time independent anomalous fluids
have been obtained by Goodeve & Whitfield (I938) and Arnold & Goodeve (1940)
using a Couette type viscometer described by Goodeve (I39 b).

I [ 1 ] Vol. 302. A. (5 December i967)

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
2 E. W. Billington
Fluids in which the individual elements of the internal structure combine to form
large particles which are not linked to form a continuous structure are those of
immediate interest; for zero flow rate this type of fluid has no detectable yield value.
The relative motion accompanying the application of a shear stress gives rise to
shear induced interactions between the suspended particles, thus producing an
increased resistance to flow.
Time dependent flow behaviour, that is the phenomenon of thixotropy, is
observed in certain types of anomalous fluid, the flow properties of which exhibit
an isothermal, reversible, time dependent decrease of the resistance to flow accom-
panying the application of a shear stress. Near steady state measurements of the
flow properties of this type of fluid (Green & Weltmann I943; Thornton & Rae I953)
do not take direct account of the time dependence of the system, though Weltmann
(I943) and Thornton (I953) have attempted to develop methods to relate breakdown
to time of shearing. The time dependent decrease in the resistance to flow of fluids
which exhibit thixotropic behaviour is effectively a transient phenomenon. Some
measurements of limited application have been made of the transient decay of the
shear stress associated with thixotropy by means of two types of coaxial cylinder
viscometer (Billington i960 a, b); the method in its initial form could not, however,
be used to observe the whole of the transient motion of the fluid.
The physical aspects of an ideal system, considered in the present paper in
relation to the Goodeve impulse theory of flow, are compared with the flow pro-
perties of two real fluids determined from a series of experiments involving the whole
of the transient motion of the fluid which is confined between rotating coaxial
cylinders. The resulting measurements enable the initial and final states of the
thixotropic fluids to be described.
A list of symbols used appears at the end of the paper.

2. SOME PHYSICAL CONSIDERATIONS FOR NON-NEWTONIAN FLOW

Consider a suspension of rigid spheres which, initially, are uniformly dispersed
in a base liquid of viscosity Yb, the continuous medium exhibiting Newtonian flow
behaviour; the spheres are of equal diameter and non sedimenting. To include bond
formation between colliding spheres consider the surface of each particle to be
covered with a number of long, semi-rigid, molecular chains the surface density of
chains being such that the major axis of each chain is approximately normal to the
surface of the sphere, the addition of the surface material producing an assembly of
spherical particles of equal diameter o. The effect of a velocity gradient 2 is to give
rise to shear induced interactions between the spheres, each interaction involving the
collision of spheres to form, in general, multi-particle aggregates; the present
discussion will, however, be limited to that of an ideal system consisting of single
spheres and two-particle aggregates composed of two interacting spheres. Each
interaction involves the formation of a two-particle aggregate together with its
subsequent motion and decay into free spheres, the latter involving the rupture of
links formed between the spheres during the initial stages of the interaction.

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonianfluid 3

2*1. The shearinducedinteraction

The generation of a multi-link bond and its ultimate rupture depend upon whether
the translational motion of the surrounding liquid can induce compression and
tension along the major axis of the two-particle aggregate during the period of its
rotation.
Bartok & Mason (I957) have shown that the rotational motion of a two-particle
aggregate formed by collision of two spheres approximates to that of a rigid ellip-
soid of axis ratio y = 2. The rotational and translational motion of interacting
particles, associated with the two dimensional, uniform, laminar flow of the suspen-
sion will be referred to the spherical polar coordinate system (r, 0, g) with the
Z-axis as the polar axis. Let the components of the fluid velocity along the (X, Y, Z)
axes be (U, V, W) respectively, such that the laminar fluid motion is defined by
(Sy, 0, 0). Consider a single prolate spheroid of major axis I to be placed with its
centre at the origin of the coordinate system. The major axis of a single ellipsoid
rotates in a spherical elliptical orbit described by the relations (Jeffery 1922)

tan O = (y2cos2q$?sin2q4) (1)

and tanq$=ytan Y2+1)' (2)

where C is the orbit constant and t' is the time of rotation. For a rigid ellipsoid the
motion of the fluid in a direction parallel to the major axis of the particle and in the
immediate vicinity of the particle-fluid interface gives rise to a force 1 directed
along the major axis of the particle. An element of the base liquid located at the
same point as that occupied by the centre of one of the spheres would have a trans-
lational velocity U = -c?gsin 6 cos? in the X-direction. The translational com-
ponent of U in a direction along the major axis of the particle UZ= oiB(0, q5)where
the orientation factor B(0, q) = sin2 6 sin q cos (3)

from which 0 can be eliminated by way of equation (1). The hydrodynamic drsag
force F, arises from the component of fluid velocity in the longitudinal direction and
as such will involve the orientation factor B, the relation for F1being of the form (see,
for example, Lamb I932; Burgers I938)
X = (Sl/_a)R(O, 4) (4)
where the effective mobility It, for flow in the direction of the major axis may vary
with S by way of the viscosity of the medium in which the ellipsoid rotates. Equation
(4) describes the particle-mobility approximation. It is evident from equation (4)
that the particle is subject to either compression or tension along its major axis
depending upon whether q5is negative or positive respectively.
Thus, during the period covering the transition from the rectilinear approach of
two free spheres to the rotational motion of the shear generated ellipsoid, the com-
pression along the major axis of the ellipsoid may give rise to the formation of a
multi-link bond between the spheres. As the ellipsoid rotates the bond is under
I-2

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
4 E. W. Billington
continuous compression up to midpoint (- = 0). With continued rotation the
ellipsoid is subject to tension along its 'Majoraxis. Rupture can occur if the tension
just exceeds the yield value of the bond.
The effect of rupturing the bond is to produce an enhanced change in the momen-
tum of the two spheres, the time dependent change in the drag force giving rise to an
impulse which is transmitted to the base liquid.
Until rupture occurs, the tension in the bond will not, in general, equal the drag
force E;. For example, although at midpoint (R = 0) the compression is zero, the
links may retain some deformation such as buckling and coiling induced during the
compression part of the cycle. Removal of the buckling and coiling will occur during
the initial stage of the tension part of the orientation cycle, only a fraction of the
available drag force F; being absorbed in this process. The difference between the
drag force F1and the tension precludes the use of equation (4), expressed in terms of
the time of rotation, for determining the impulse.
Goodeve developed the impulse theory of flow for the translational motion of a
single link by assuming Hooke's Law for the extension of the link. It is necessary,
however, to recognize that a multi-link bond may exhibit non-linear elasticity.
At any given time t, of deformation of the bond assume the rate of strain c(tj) in
a single link to be related to the tension fL(t) in the links by the relation

e(6) [= K (x f(t) -
]i (5)

where, for example, in the Eyring reaction rate theory (Eyring et al. I964) k is the
Boltzmann constant, T the absolute temperature and K, a function of molecular
parameters, is the absolute rate in the absence of an applied tension. The charac-
teristic length x is the distance that a segment of a chain molecule moves in the life
time TL of the link. Equation (5) differs from the usual form in which Eyring's
reaction rate theory is expressed, by the omission of a rate component involving
fL(t6) in the reverse direction. The application of Eyring's theory of rate processes
to the behaviour of systems similar to the multi-link bond has been discussed by
Halsey (I947) and Meredith (I958).
The total impulse from the bond is obtained from equation (5) in the form

1e(6o0q) = f FLdte= NL(09O I

500) |ln (l + et) dt6, (6)

where FL(t6) = NL(QO, 00) .fL(tJ), the number of links NL being taken to be propor-
tional to the drag force FCat impact; (00, 00) is the initial point of contact. The multi-
link bond has been approximated to an assembly of NL identical long chain mole-
cules distributed about the major axis of the ellipsoid (this approximation implies
that the curved surfaces of the spheres are to be regarded as parallel plane surfaces
in the region of link formation).

2*2. The lifetime and concentration of ellipsoid8

An ellipsoid is generated from the shear induced interaction of two spheres, the
initial point of contact (00, 00) defining by way of equation (1) the orbit constant C

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonianfluid 5
for a given value of y. The fraction of collisions in the interval dOodoo at (00,00) is
(Manley & Mason I952)
g(00,00)dOodoo = 3 sin300 sin 00 cos q0dOodoo, (7)
the limits of 00 and ?s0being taken to be 0 to 17T.
From equations (2) and (7) the mean
value of the time for which the ellipsoid is under compressionis

TC
= 4+1)-j:
J
tan' (tan 00 g(0O,00) dOodoo =

for y = 2. For an interaction which is symmetric about the midpoint (R = 0), the
total life time of an ellipsoid 51T 1(
yre- 6 . (8)
Two types of momentum carrier can be distinguished in the form of the spheres
and the ellipsoids, the instantaneous distribution of carrier densities being given by
the continuity equation which for either species has the form

atn/lt = (Qs-Qe)V- . n V,

where V is the translational velocity of a particle, Qsis the net rate of generation and
Qethe net rate of decay of the n-type species. The shear induced interactions give
rise to ellipsoids which are characterized by their mean life time ze' leading to the
generation of an ellipsoid density such that at some time t of shearing and for a
givenS N= n8+2?,

where n8 and ne are the densities of free spheres and ellipsoids respectively and N, is
the total number of individual spheres per unit volume. The rate of change of free
spheres due to shear induced collisions will be taken to be ns/;r where the life time
Tsof the spheres is related to the collision frequency per particle qs, associated with
the shear induced interactions in such a way that n8/T8is the two body collision
frequency per unit volume Qs. Similarly the rate of change of ellipsoids due to shear
induced interactions will be taken to be ne/Ye*Thus for the ellipsoid density, the
equation of continuity has the form
dn, _ n, (10)
dt %Te 'r

where for conditions of uniform, two dimensional, laminar shear flow the contribu-
tion arising from the particle current density per unit mass (ne Ve)has been taken to
be zero; in equation (10) the effect of Brownian motion on the spheres has been
neglected. For conditions of steady shear, equilibrium will exist between the
generation and decay of ellipsoids such that

ne, = TenslTs_ (I11)

For a suspension of spheres, taking into account the formation of ellipsoids but
neglecting in the first approximation the effect of Brownian motion on this process,
the shear induced collision frequency per particle qs was shown by Smoluchowski
(I9I6, I9I7) to be q 3=n,S (12)

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
6 E. W. Billington
and the two body collision frequency per unit volume Q8is 1q,n8, which combined
with equations (9), (11) and (12) yields for steady shear the equilibrium condition

2= 0o3(1N -2nfe)2 SAe, (13)

from which it is evident that the variation of the ellipsoid density ne with S is solely
dependent upon the way in which the product T, varies with S (provided the
collision cross-section is independent of S). For an interaction which is symmetric
about the midpoint (1 = 0), equation (8) combined with equation (13) yields an
ellipsoid density which is independent of S.

2-3. The rheological equation of state

The total force per unit area due to rupture of links is the Goodeve stress (Gillespie
I 960) Se-fi=8I1 sin 00 sin 00, (14)

where the point at which rupture occurs has been taken to be the mirror image point
of contact, ,8 is the rate at which impulses are generated per unit area and Ix is the
component of the total impulse which is effective in the direction of flow. At any
given instant only a fraction dne of the ellipsoid density ne will be contributing to Pe
by way of the impulse I,. In equation (10) the rate of decay of ellipsoids per unit
volume has been taken to be neI/e; thus the mean rate at which impulses are
generated per unit area relative to the area occupied by an interaction will be taken
to be approximately given by
dnei0n?i0
,8 = TI sin 00 cos 00 - sin 00 cos 00,
T-1 (15)
TL ~~~~Te
where I sin 60 cos 00 is the separation of the two parallel shear planes (Goodeve
I949). The total stress Pe is obtained from equations (14) and (15) in the form

Pe = -le(O,lVo)R(0O0,
q) g(Oo,q0) dO0doo, (16)
Te so ()

where R(00qo,), Ie and Y(Oo,00) are given by equations (3), (6) and (7) respectively.
The viscosity ?qof the suspension is defined by the relation

P =- '9(17)
for all S~,the viscosity in general varying with #.

According to Goodeve (1939 b) the total force per unit area can be expressed as

P=Pe+P1 (18)
thus yielding the rheological equation of state for the fluid.
A rheological equation of state which has been found to have application for
certain types of anomalous fluid can be obtained by specifying the time dependence
of the rate of strain 6(tj) and the flow rate dependence of ?Y.
At any given time t, of deformation of the bond assume the rate of strain

6(tj = bASItJTL, (19)

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonianfluid 7
where the constant b, which is taken to be independent of AS, is evaluated by inte-
grating equation (19) to yield the strain
bS-- =L(t6)
VJ=,- trL =9

and noting that for t, = -rL, the extension of a link X= 6L(rL) such that

b= (20)
LOSrL
where Lo is the original length of the link at t, = 0. Combination of equations (19)
and (20) yields 2X S t
6 -t-S-aO , (21)

where TL = K/S (22)

is to be compared with equation (8), K being independent of both S and the orienta-
tion of the ellipsoid in order to maintain b independent of S.
Introducing e(t) from equation (21) into equation (6) yields

1e(OO,S00)= NL(OO L(+A ) [1n1(1+ AS) -> (23)

where A (24)
KL0K
is independent of S.
The relation obtained by Vand (I 948) for the viscosity of a suspension of spheres
and shear generated ellipsoids can be expressed by way of equation (9) in the form

Y = Ys+Ye) (25)
where Ve= 'lbe e

and VS = Ybll+ V' s(Ns-2ne)],

where for non-link forming ellipsoids Vfsand fe are independent of S being solely
dependent upon the type of particles present in the suspension (Manley & Mason
I954; Mason & Manley I956; Nawab & Mason I 958). For a given AS the viscosity of a
suspension of link forming ellipsoids will be taken to be of the form

=s + o
.-Y (26)

where Yo= Ap. (27)

n
and - .elkTrL(I + AS) { J NL(Oo, S0)R(OO,S0)g(0o, S0)dOodoo. (28)

The component Y- VYof equation (26) is associated with the ellipsoids and the
component Y8has the same significance as that of equation (25). A relation of the
form of equation (26) has been generally observed (Mooney I95I; Gillespie I960)

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
8 E. W. Billington
to represent approximately the viscosity of concentrated high polymer solutions
as a function of flow rate.
Taking NL(Oo,00) to be proportional to the drag force FCat impact yields by way
of equation (4)
NL(OO) M)0)= E1MC= E R(0oO00)~ (29)
= EI~= jIte
where the effective mobility Pe can be expressed in terms of the equivalent sphere of
radius 0e in the form (Lamb I932)

=
6 G (30)
the viscosity Ye for the purpose of the present discussion being identified with the
component I - V of equation (26). From equations (26) and (30)

Ite- = 0 +)(AS), (31)

the link density NL(Oo,00) being obtained from equations (29) and (31) in the form

NL(OO,
00) = No (1 R (00, 00) (32)
(1 + AS)
where NO(= El/Ap0) is independent of the orientation of the ellipsoid and of S.
00) from equations (6), (21) and (32) into equation
Introducing In, e(tJ)and NL(OO,
(16) yields pe [ln(1?A@)_(AS ], (33)

where from equations (8), (22), (28) and (32)

= 24nlelNK kT (34)
175:7rX
which is independent of S.
The curved surfaces of the spheres have been approximated to plane surfaces in
the region of link formation so that the NL links can be regarded as identical.
However, in practice the increase in the link density arises from the decrease in the
major axis I of the ellipsoid as S9increases. With increasing ASthe major axis 1attains
a minimum value (Mooney 1957) for a particular value of the velocity gradient Sa.
For S = $a the link density attains a saturated value Na which is maintained for all
S S. Thus two types of bond can be distinguished; the unsaturated bond corre-
sponds to (0 < i < Sa) and the saturated bond corresponds to S > Sa
The rheological equation of state for an unsaturated bond is obtained from
equations (17), (18), (26), (27) and (33) in the form
p = pjIn(I+AS)+yS (?AS Sia) (35)
where pa is given by equation (34).
From equation (35)
dp AP (6
dS ( l + AS) + Vs = v (OS< <SSa) (36)

from which it is evident that for an unsaturated bond the differential coefficient of
viscosity is identical to the viscosity as defined by equation (17). This is of particular

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonianfluid 9
interest in so far as this condition permits the viscosity to be determined directly
from experiment, in contrast to the often observed situation in which there is
introduced an apparent viscosity defined as p/S which has no fundamental signi-
ficance for the material (Oldroyd I956). For conditions of saturation, a rheological
equation of state which is formally similar to that of the ideal Bingham plastic can
be obtained by extending the concept of a differential coefficient of viscosity for the
range S > Sa. For the ideal Bingham plastic the viscosity is independent of S,
integration of the differential coefficient of viscosity yielding

P=Pa+Y1=Pa+(Y1a+Ys)iS (S> Sa), (37)

where 'la is the component of the viscosity associated with the presence of the
ellipsoids for conditions of saturation. For the flow properties to be continuous in the
region of Sanequations (35) and (37) yield the condition

Pa = P In(1 +
ASa)-yVa San (38)
which is independent of S.

3. EXPERIMENTAL
Fluid A is prepared by adding at ambient temperature a given concentration of
aluminium laurate to a Newtonian oil of viscosity 35- cP at a temperature of 37-8 'C;
a small concentration of m-cresol is added to stabilize the fluid. The temperature is
increased to 80-0 C, the system being continuously stirred at this temperature for
ten minutes. As the temperature is reduced the viscous property of the fluid
increases appreciably producing at ambient temperature a fluid which exhibits
marked visco-elastic behaviour. The resulting fluid has been obtained in two forms,
both of which depend upon the properties of the aluminium laurate, one form (A2)
exhibiting the phenomena of thixotropy in contrast to the other (Al), the flow
properties of which are time independent.
Fluid B is a colloidal suspension of graphite particles dispersed in a Newtonian
oil of viscosity 119cP at a temperature of 37-8?C; the concentration of graphite
particles is 13 g per 100 g of the bulk component. From electron micrographs it has
been established that approximately 95 %of the graphite particles do not exceed
1 yim in diameter, the remaining 5 %are mainly in the range 1 to 5 yim. Separation of
the two phases, because of such effects as sedimentation, has not been detected over
very long periods of standing at ambient temperature.
The viscometer used in the present measurements has been described (Billington
I965) together with its use to determine the flow properties of a series of Newtonian
lubricating oils for conditions of steady state, transient and oscillatory motion.
For the transient motion the outer cylinder is taken to rotate at constant angular
velocity w0for all time t of shearing the resulting transient motion of the inner
cylinder being characterized by the limiting conditions (t = 0, w(Oi()= w00)and
(t = oo, woi(oo)= 0), where cl) is the angular velocity of the inner cylinder. At some
time t of shearing the shear stress
=
pi(t) ^o*(t) (39)

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
10 E. W. Bilington
measured at the wall of the inner cylinder of radius r*is correlated with the flow rate
@*(t)defined by the relation
2r2 ~ dt
2
(??-d) = hi(oo- o(t)), (40)
(r2_;d
where Oi(t)is the angular displacement of the inner cylinder, ro is the radius of the
outer cylinder and 4gT2r2H

where MOis the restoring couple per unit angular displacement of the inner cylinder
of height H. The angular velocity cl)(t) is obtained by graphical methods from the
(0, t) curves.
The correlation by way of S~i(t)defined as for the flow of a Newtonian fluid does
not imply that AS*(t)can be identified as the rate of shear at the wall of the inner
cylinder, the use of equation (40) being merely a convenient way of expressing the
change in p*(t) with (woo- wl)(t))for the three cylinder gap widths in use. This applies
to both the steady state and transient flow of the fluids. In general the present type
of measurement cannot be used to establish the form of the rate of shear, as measured
relative to the wall of the inner cylinder, for the flow of non-Newtonian fluids.

4. EXPERIMENTAL RESULTS

The measurements for fluid A have been confined to cylinder gap widths for which
ro = 2-38 cm, the change in the shear stress pi with S* being determined for three
values of r*.
For fluid Al examination of the measured values of p*(oo) plotted against S*(oo)
in figure 1 for several values of the concentration c shows that for the steady state
the experimental results for the three values of ri can be represented by a single
curve for each value of c.
Examination of the measured values of the stress p*(t) plotted against the time
of shearing t in figure 2 for a given ri shows that only part of the transient motion,
represented by the full line curves which extend from t = 0 to t = tb, can be corre-
lated with @*(t)by way of equation (40). These curves are typical for fluid A2. The
stress p*(t) is plotted against S*(t) for the range (O < t < t,,) in figures 3 and 4 for
fluid A2. The full line curves shown in figures 3 and 4 are identical, from which it
follows that the individual (p*(t), 2*(t)) curves corresponding to the several values
of wo0and the three values of ri all compound together to yield a single (pi, S*) curve
as observed for the steady flow measurements of fluid Al.
For t > tb the quantity S*(t) increases more rapidly than is required for the
correlation over the initial range of time. The change in flow behaviour in the region
of tb is attributed to the onset of thixotropic behaviour of the fluid. With continued
shearing the inner cylinder comes momentarily to rest and then begins to rotate in
the opposite direction to that of the outer cylinder; after a long time of shearing the
inner cylinder comes to rest corresponding to the steady state flow of the fluid. The
final steady state values of the stress p*(oo) are shown plotted against Si(oo) in

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonianfluid 11

400 sa

300- , C(=4%
-750

100 = _ = f 500

3%~~~~~~C

100- ~~~~~~~~~~~~~~~

0 5 10 15 20 25
Si(00) (SW)

FIGURE 1. Concentration dependence of the shear stress pj(oo) relative to SA(oo)for the three
values of ri for fluid A 1.
A, 1F90cm; 0, 2-06 cm; l, 2-22 cm.

3000 flF'-

\O 0OO
0
225 -

7G ,0_ *f .
~~150 oOab~~~~~0 00 000 0 0 0

75-

0 5 10 15 20 25
t (s)
FIGURE2. Typical examples of the variation of the shear stress pi(t) with the time of shearing
for several values of woand ri = 2-06 cm for fluid A 2.
A, 0 06radsL; Ol,O lrads-1; +,021rads-1; 0, 042rads-1;
V, 0-84 rad s-; 0, 1-26 rad s-; C), 1I*68rad s'.
This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
12 E. W. Billington

Se Sa(O) Sa0oo)
300_

(Pi, ) ,,)

f ~~ ~
~~~~20 30
~~ ~ 40

0 5 10 15 20 25
Si (s-')
FIGURE 3. Variation of the shear stress pi with Si for various values of ri for fluid A 2.

O, , 2-22cm; A, A, 1-90cm; ,2-06cm.

,Se -Sa(O) S(OO)

300 _

I~~~~~~~~~~~~~~~~~~~~~~~~~~~i
I I.

200 (PI
. ), S ) S (s-i)
. g~~~~~~~~~~,

0
l l ~~(Pl 00.
l ) l

0 5 10 15 20 25

FIGURE 4. Variation of the shear stress pi with ii for several values of (00and ri = 2-06 cm for
fluid A 2.
0, 0O21rad s-1; E1,0-63rads-1; A, 1b05rads-1;
1O, b68rads-1; V, 2.1 rad s-1; x , St(t) for t > tb.

figures 3 and 4 for the three values of ri, the results being represented by a single
curve.
The rotation in opposite directions of the two cylinders has been consideredfor
the unsteady flow of a Newtonian liquid (Billington I965), it being shown that the

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonian fluid 13
rate of shear can still be obtained from equation (40) by replacing O)i(t)by - O)(t).
The transient change inp*(t) with S*(t) for t > tbis shown in figure 4 for several values
of o0 and r* = 206 cm. These results are typical for all three values of r*.
Owing to the onset of thixotropy the maximum value Pm which the stress p*(t)
attains for a given o0 falls short of the value p*(O) which it would attain in the
absence of thixotropy. For a given o0 the stress p*(O) can be obtained from the
(pi, S*) curves of either figures 3 or 4. The ratio p*(t)/pi(O) is plotted against t for
the three values of ri and the same value of S*(oo) (-hi o)0)in figure 5 for fluid A2.

10

0 2 4 6 8 10
t (s)
FIGTURE 5.Effect of cylinder gap width on the variation of the shear stress pi(t) with the time
of shearing for the three values of ri for fluid A 2 (ro= 2 38 cm.).
0, 1.90 cm; A, 2-06 cm; El, 2 22 cm.

The fraction of the (p*(t), t) curves obtained prior to the onset of thixotropy is seen
to increase with increasing cylinder gap width for r0 a constant from which it follows
that extrapolation to zero gap width will not yield the true (pi, S*) characteristic
(cf. Lindquist & Sierichs I950).
The transient and steady state changes in the shear stress with S* have been
determined for fluid B using an outer cylinder for which rO = 11 1 cm. The (p*(t),t)
curves for fluid B are similar to those for fluid A2, differing only in the magnitude
of the stress which, for similar values of A*, is much greater for fluid B. The stress
p*(t) is shown plotted against S*(t) in figure 6. As for fluid A2, the individual
(p*(t),2*(t)) curves corresponding to the several values of w0and the three values of
r* all compound together over the range 0 to tb to yield a single (pi, S*) curve.

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
14 E. W. Billington
Comparison of figures 3, 4 and 6 indicate that the 'shear stress-rate of flow'
characteristics of fluid B are formally similar to those of fluid A2. The steady state
values of pi(oo) are also shown plotted against S*(oo) in figure 6, together with the
variation of p*(t) with S*(t) in the range of the time of shearing from tb to oc. For
fluid B the maximum value of the ratio (p*(t)/p*(O)), increases with increasing
cylinder gap width in a similar way to that shown in figure 5 for fluid A 2

S~e Sa(O)
S~a(a:0)
l l I
3000

(pb(o), s(o)) xxX__>

n 2000 -

1000 ,r

I I I I I.I
0 25 5 75 10

FIGURE6. Variationof the shearstresspi with @ for four values of ri for fluid B.
U, o, 0-52cm; A, 0, 0 63 cm; * , 0-79cm;
A, 0-95 cm. ,
x %(t)fort> tb.

5. ANALYSISOF RESULTS
From figure 1 it is evident that for fluid Al the (p*(oo),S(oo)) curves consist of
two distinct regions, the change in flow behaviour occurring at S'a. In the region
(0 < Si(OO) < SO)the full line curves of figure 1 have been obtained from equation (35)
using the values of the parameters pa and A given in table 1, the closest agreement
between experiment and the proposed rheological equation of state being obtained
by taking 'q8= 0 for all S* and for all values of c. For (Si (oo) > Sj) the full line curves
of figure 1 have been obtained from equation (37), the values of the parameters 'ql
andpa being obtained from table 1 andy8 being taken to be zero for all S in order to
satisfy the condition that the flow properties shall be continuous in the region of S,
From figures 3, 4 and 6 it is evident that fluids A2 and B can exist in at least two,
distinguishable, rheological states for values of Si greater than a critical value Ser
In order to distinguish the two rheological states, the flow properties prior to the
onset of thixotropy will be characterized in the form (pi(O),Si(0)), which is taken
to cover the whole range of S*, and in the form (pi(oo), *(aoo)) for the final steady
state covering only the range of Si for which S*(O0)> Se.

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonianfluid 15

TABLE 1. CONCENTRATION DEPENDENCE OF THE FLOW

PARAMETERS FOR FLUID A
C P~a A Va Ya Pa
(%) (dyn cm-2) (s) (s') (P) (dyn cm-2)
2 26*5 0*22 15.1 1*5 15
3 27*5 2*6 10*0 2-9 66
4 3192 547 7-3 4-3 228
5 35-4 106 5*5 6-3 410

Examination of figures 3, 4 and 6 shows that the (pi(O),SA(O))curves consist of

two distinct regions the change in flow behaviour for the fluids in this state occurring
at 6a(O). In the region 0S < Aa(O)) the full line curves (pi(O),S(O)) have been
obtained from equation (35) using the values of the parameters Pa = pa(O)and
A = A(O)given in table 2, the closest agreement between experiment and the proposed
rheological equation of state being obtained by taking ', = 0 for all Si. For
(S > Aa(0)) the full line curves (p (O),SA(0))have been obtained from equation (37)
for the values of the parameters 'qa = Ya(0) and Pa(O)given in table 2, y8 being taken
to be zero for all )%in order to satisfy the condition that the flow properties, before
the onset of thixotropy, shall be continuous in the region of ASa(O).

TABLE 2. FLOW PARAMETERS FROM TRANSIENT TYPE MEASUREMENTS

FOR FLUIDS A 2 AND B

JPa A 'a Sa Pa
fluid (dyn cm-2) (s) (P) (s-') (dyn cm-2)
A2 (0) 69*5 3-77 9*2 7*0 170
A2 (oo) - - 22 15.4 151
B (0) 540 14*7 286 1*9 1280
B (oo) 430 9-5 104 4.2 1170

The value of S(t) having been obtained, and hence the flow parameters p,(O), A(O)
and Ya(0), by graphical methods, the correlation between experiment and the
proposed rheological equations of state can be further verified by calculating the
value of A?(t) for a given value of the stress p,(t). For a given value of )00,the transient
measurements yield a series of experimental values of 6i(t) and t which are photo-
graphically recorded using the same camera. For the transient motion and
(O < Aqi(0)< Sa(O)) the relation
S~(t) = Si~(0c) [1 - exp (- tITm)] (42)
A
[1I+ (0) A% -
(c) exp ( tITm)]

where TM= PA() S((oo)) 6 = ve(0)6 (s =0) (43)

can be obtained, 6 being given by equation (41). By usinig the experimental values
of t, the required value of SA(t)can be calculated from equation (42), the values of
the parameters pa(O) and A(O) having been obtained by the graphical method.
Although the parameters pa(O) and A(O)are determined by graphical methods it is

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
16 E. W. Billington
the actual experimental values of the stress pi(t) which are shown in figures 3, 4
and 6, the corresponding values of S~i(t)having been calculated from equation (42)
for the experimental values of t and the graphically determined values of the
parameters pa(O) and A(O).
For AS~(O)> AS,a(0)it has been found that the flow rate can be expressed in the form

Si(t) = SA(oo)- (i(o) -a(0)) exp (- r-())

T
(44)

where TI = a(0) 6 (s8= 0) (45)

and ta(O)is the time corresponding to which fi(t) = Sa(O). Using the experimental
values of t, the required values of Si(t) can be calculated using the value of Ya(0)
obtained by graphical methods. It is these values of SA(t) and the corresponding
experimental values of pi(t) which are shown in figure 3, 4 and 6.

1250r-

40 1000

30- 750-

~z20 -500,

10 250

0 1 2 3 4 0 025 05 075 1-0

t (S),
FIGURE 7 FIGURE 8
FIGU:RE7. Variation of p(t)/it(t) with the time of shearing for the three values of ri for fluid A 2.
A, 1F90cm; 0, 2-06cm; ro,2*22cm.
FIGU:RE8. Variation ofpj(t)/Si(t) with the time of shearing for three values of w0and r- = O-79cm
for fluid B. a, 0 42rads-1; 0, 1b26rads-1; A, 2-1 rad s-1.

For fluid A2 the time interval required to restore the flow properties, in particular
to recreate the maximum observed displacement 0m is about 30 s for all SAcompared
with about 30 min for fluid B. Examination of the measured values of the ratio
(pi(t)/1A(t)) plotted against the time t of shearing, for (tb < t < oo), in figures 7 and 8
shows that the time occupied by the transition from the initial to the final steady
state is comparable with the time taken to recreate Omfor fluid A2, but is considerably
less than the 30 min required to recreate 0m for fluid B.
From the concentration dependence of the flow parameters given in table 1 for
fluid Al, it is evident that Pa increases with decreasing Sa and that A increases

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonian fluid 17
rapidly with decreasing Sa* Assuming that the change in state associated with the
thixotropic nature of the fluid A2 is related to a change in concentration of the
ellipsoids, the concentration dependence of the flow parameters for fluid Al may
provide an indication of the behaviour expected from fluid A2 during the transient
change in state. Taking the change of the steady state values of pa = pa(oo) and
A = A(oo) with Si(oo) to be of the form

"X0) a'0 0-A iSi(oo) -Se) (46)

and A(co) = A()) ()

[1 + AeO(00(O) - ~9e)]' (7

where A. and A, are independent of S*(oo), satisfies the limiting conditions at

A%(oo)= Sn, and the condition that pa(oo) and A(oo) should both decrease with
increasing Si(oo) as observed for the concentration dependence of the flow para-
meters p0cand A on Safor fluid Al. Replacingp<, and A in equation (35) by pJoo) and
A(oo) yields the relation

pi(oo) = pa(ao) ln (1 + A(oo)Si(oo)) (Vs= 0),

from which the full line curves of figures 3 and 4 for the final steady state have been
obtained using values of Aa = 0 345 and A, = 1-05 x 10-2 s. From figure 3 it is
evident that for A%(oo)> Se the (p*(oo),Si(oo)) characteristic exhibits a change in
flow behaviour in the range of S*(oo) =Sa(O0), the (p*(oo),S*(oo)) characteristic for
S*(oo) > Sa(oo) being of the form given by equation (37); the values of the parameters
Ya(oo) and SA(oo)are given in table 2.
For fluid B the parameter A is assumed to decrease from its initial value A(0) to
a minimum value A(oo), both values of A being taken to be independent of S*. The
change in A will give rise to a change in p6,, the steady state value P6(oo)being
independent of S*(oo).Thus the steady state flow properties of fluid B, for S*(oo) > S9
will, in terms of the impulse theory of flow, be described by a (p*(oo),S*(oo)) charac-
teristic of the form of equations (35) and (37). The full line curve shown in figure 6
for the steady state condition has been obtained from equations (35) and (37) and
the values of the parameters p,(oo), A(oo) and Ya(OO)given in table 2.

6. DiscusSION AND CONCLUSIONS

The use of the quantity SA, defined by equation (40), has yielded a satisfactory
degree of correlation between p*(t) and (o)o- co1(t))for the three cylinder gap widths
in use. In particular the maximum discrepancy between any one of the three values
of the shear stress, corresponding to the three values of r*, and the full line curves of
figure 1 for a given value of S*(oo)does not exceed + 2 % over the available range of
S*(oo) for c > 2 %. The maximum discrepancy for c = 2 % decreases from ca. 17 %
(corresponding to a difference of 1 dyn cm-2), to ca. 2 % as AS(00)is increased from
1 to 26 s-1. For fluids A2 and B corresponding to their initial rheological state the
majority of the individual measurements of p*(0) for the three values of ri compound

2 Vol. 3o2. A.

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
18 E. W. Billington
together about the full line curves to within + 2 %for both fluids. However, the
maximum observed discrepancybetween the three values of pi(O)and the full line
curves for a given value of SA(O)is greater for both fluids, being of the order of 3 %
for fluid A2 and of the orderof 4 %for fluid B. The flow propertiesfor fluids A2 and
B, correspondingto the finalsteady state, aresuchthat the majority of the individual
measurementsof pi(oo)for the three values of ri compoundtogether about the full
line curves to within + 2 % for both fluids; however, the maximum observed
discrepancy between the three values of pi(oo) and the full line curves for a given
value of Si(oo)is considerablygreaterfor both fluids at low values of soo,being of the
order of 5 %for fluid A2, the correspondingfigure for fluid B not exceeding 6 %.
For t > tbthe rate at which the stress decreaseswith the time of shearingincreases
as 0ois increased.Thus in a given time interval measuredrelative to tb,the propor-
tional decrease in stress increases with increasing (o, and as such the time interval
allowed for the stress relaxation to reach its minimum may, in some instances, have
been insufficientparticularlyfor low values of (oo.In this connexionisolated samples
of both fluids were continuously sheared for several hours at low values of 00, the
final values of pi(oo) agreeingto well within 2 %with the full line curves.
To establish the significanceof Si in relation to the rate of shear at the wall of the
inner cylinder would require direct measurement of the velocity at various points
across the gap between the viscometer cylinders. Such measurements, however,
require the introduction of some form of ancillary detecting probe (Richardson &
Tyler 1933), and are therefore open to the objection that the presence of the probe
would disturbthe flow conditionsin the sample.Using a coaxial cylinderviscometer,
Lindquist & Sierichs (I950) made their measurementsin such a way that an extra-
polation to zero gap width between the cylinders could be made; it is evident from
figure 5 that such a proceedurecan not be applied in the case of fluids A and B. It
has, however, been possible to measure the velocity, using a miniature propeller,
at variouspoints across the diameter of a pipe (Billington, Jones & Wyllie I962),
through which a thixotropic fluid D was flQwingat a relatively low temperature,
the ratio of pipe diameter to propeller diameter being approximately 20:1. From
the measurementsit was concludedthat the velocity profileswere parabolic at the
observed stages of the transient decay in stress. The flow properties of the same
fluid have also been measured with a coaxial cylinder viscometer (Billington
ig6o a, b), the stress correlatingwith the angular velocity by way of equation (40),
which observation,taken together with the pipe flowmeasurements,'tendsto suggest
that for fluid D the quantity Si measured at the wall of the inner cylinder may be
taken to be the rate of shearas for the flow of a Newtonian fluid. Fluid D differsfrom
fluid B in that the minority component of fluid D consists of aggregates of wax
crystallites.
It has been shown for the particular,ideal system of immediate interest that the
differential coefficient of viscosity, as given in equation (36), is identical to the
viscosity associated with the component of stress appearing in equation (17).
Arising from this is the observationthat the slow transient motion of the anomalous
fluids is characterizedby the time constants Tm and r. given in equations (43) and
(45), which have the same formal dependence upon the viscosity, for a given Si, as

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonianfluid 19
the time constant which characterizes the transient flow of a Newtonian fluid
(Billington I965). This formal similarity between the flow properties of the ano-
malous fluids as determined from the transient type measurements and the corre-
sponding flow properties of Newtonian fluids in relation to their dependence upon
the visposity is of interest with regard to the observed correlation of pi with Si,
where Si is defined to be formally the same as the rate of shear associated with the
flow of a Newtonian fluid as given by equation (40).
The analysis of the measurements using the transient motion depends upon two
conditions. The moment of inertia Ii of the inner cylinder must be sufficiently small
so that the couple Ii Oican be neglected; also the contribution from the inertia of the
fluid must be negligible. If these conditions are not satisfied, the inner cylinder will
have at t = 0 an angular velocity less than that of the outer cylinder. For all
measurements described no difference could be detected between the angular
velocities of the inner and outer cylinders at t = 0.
The degree of correlation between pi and Si obtained by setting y- = 0 in equa-
tions (35) and (37) implies that although m,cannot be zero, it must be sufficiently
small for it to make a negligible contribution to pi over the available range of S*.
At any given instant the rupture of the bond joining the spheres of the ellipsoids
produces an initially localized perturbation of the hydrodynamic flow pattern of the
continuous medium; each disturbance expands to produce a communal effect which
will modify the viscosity of the continuous medium and therefore the viscosity y8
will be expected to be flow rate dependent in the range (O < S < Sa) The apparent
inability to detect any such effects is attributed to the magnitude of 'I, which is very
much less than e.
In developing the rheological equations of state the effect of Brownian motion
has been neglected. The collision frequency per particle qB due to Brownian motion
was shown by Smoluchowski to be 8n, 1TI3y1 which can be combined with equation
(12) to yield the ratio S.
q8IqB This, however, has the formn&Oc3/2kTwhich is seen to
involve the effective viscosity yc of the continuous medium in which the singlets are
dispersed. Since j, and therefore also n, have not been evaluated it follows that the
effect of Brownian motion cannot be evaluated (for c= 'lb it follows that for
fluid B the ratio qJ/Bq - 14s).
For fluids A2 and B the initial flow properties determined from transient type
measurements do not exhibit any form of transient decay of the stress and as such
the flow properties for Si < Se are taken to refer to their rheological state corre-
sponding to maximum particle size and maximum surface interaction of colliding
particles, prior to the onset of the thixotropic behaviour of the fluids. For S* > Se
the transient measurements yield an extension of the (p*(O),S*(O))curves which are
continuous in the region of Senthe whole of the available range of the (p*(O),SA(0))
curves for fluids A2 and B, together with the (p*(oo),S*(oo)) curves for all values of
the concentration c for fluid Al, showing close agreement with the proposed
rheological equations of state.
The thixotropic behaviour exhibited by fluids A2 and B may arise from the
rotational motion of the free spheres. Consider an individual sphere to be placed with
its centre at the origin of the coordinate system. For two dimensional, uniform,
2-2

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
20 E. W. Billington
laminar flow Qz = I,rMT, where MT is the moment of the forces exerted on the
particle by the translational motion of the surrounding liquid, Itr is the rotational
mobility and Qz (= 'S) is the angular velocity of the sphere about the Z-axis.
Associated with the rotational motion of the sphere is a centrifugal force which
subjects the surface layer of long chain molecules to a tension which can, in principle,
exceed the strength of the bond holding the surface material in place. Such an effect
will be first detected at some particular value Se of the velocity gradient. Once
started the process of removing the surface material will be continuous since, in
general, after each shear induced interaction the sphere will begin to rotate about
the Z-axis in a different orbit in relation to the material which is initially detached.
Thus fluids which exhibit this type of particle behaviour will be distinguished by a
discontinuity in the (pi, Si) characteristic in the region of Se of the form shown in
figures 3 and 4. This arises from the decrease in cross-sectional area of the spheres
and, in general, from a reduction in the surface density of potential linkage points
which in turn reduces the total impulse.
For the transient, rotational, motion of an individual sphere the equation of
motion can be expressed in the form

Zdzdt
dtz
=i - MT- TI z (48)

wherejz is the moment of inertia of the particle about the Z-axis (coupling between
translational and rotational motion in relation to structured continua has been
considered by Dahler & Scriven I963). It is evident from equation (48) that for
transient motion, thixotropic behaviour will occur when MT exceeds Me(= SeI2/1r)
by an amount jz(dQz/dt). Thus for the transient motion in use the flow rate at which
thixotropy first occurs can, in principle, be made to exceed S~e.For transient rota-
tional motion of individual spheres there is also the possibility of a strain-rate
dependent increase in the yield stress of the links which may also yield a flow rate
greater than Se at which thixotropic behaviour would occur.
The experimental method for determining the transient decrease in resistance to
flow, arising from the thixotropic nature of the fluid, is subject to one particular
disadvantage is so far as the measurements are not made at constant SA. The
behaviour associated with the Weissenberg effect is not exhibited by either of the
fluids over the quoted range of Si. For fluid A, behaviour associated with the
Weissenberg effect has, however, been observed for Ai considerably in excess of the
highest values quoted in the present measurements whereas no effects of this type
have been detected for fluid B.
It is evident that the Goodeve impulse theory of flow can be applied to the flow
properties of fluids whose physical and chemical properties are widely different,
and in particular provides a simple way of introducing the internal rotational
motion of the individual particles of the minority component. For fluids which
exhibit the phenomena of thixotropy the transient type of motion enables measure-
ments to be made which extend the 'shear stress-rate of flow' characteristics
over a wide range of stress, corresponding to the rheological state of the fluids prior
to the onset of the time dependent decrease in the resistance to flow associated with

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow propertieesof two types of non-Newtonianfluid 21
the thixotropic nature of the fluids. This is in contrast to previous methods of
analysis which in general only yield information relating to the final steady state,
or some intermediate, arbitrary, state of the fluid.

REFERENCES

Arnold, J. E. & Goodeve, C. F. I940 J. Phys. Chem. 44, 652.

Bartok, W. & Mason, S. G. 1957 J. Colloid Sci. 12, 243.
Billington, E. W. Ig6oa Proc. Phys. Soc. 75, 40.
Billington, E. W. i96ob Proc. Phys. Soc. 76, 127.
Billington, E. W. I965 J. Sci. Instrum. 42, 569.
Billington, E. W., Jones, J. T. & Wyllie, D. I962 J. Mech. Enyng Sci. 4, 308.
Burgers, J. M. I938 Second report on viscosity and plasticity, pp. 113-184. Amsterdam:
Academy of Sciences.
Dahler, J. S. & Scriven, L. E. I963 Proc. Roy. Soc. A 275, 504.
Eyring, H., Henderson, D., Stover, B. J. & Eyring, E. M. I964 Statistical mechanics and
dynamics, p. 447. New York: Wiley.
Gillespie, T. I960 J. Colloid Sci. 15, 219.
Goodeve, C. F. 1938 Rep. Progr. Phys. 5, 20.
Goodeve, C. F. I939a J. Sci. Inst. 16, 19.
Goodeve, C. F. I939b Trans. Faraday Soc. 35, 342.
Goodeve, C. F. I949 Proc. Intern. Rheol. Congr., Scheveningen, 2 A, 5.
Goodeve, C. F. & Whitfield, G. W. 1938 Trans. Faraday Soc. 34, 511.
Green, H. & Weltmann, R. N. 1943 Industr. Enyng Chem. 15, 201.
Halsey, G. 1947 J. Appl. Phys. 18, 1072.
Jeffery, G. B. 1922 Proc. Roy. Soc. A 102, 161.
Lamb, H. 1932 Hydrodynamics (6th ed.), p. 605. Cambridge University Press.
Lindquist, C. G. & Sierichs, W. C. I950- J. Colloid Sci. 6, 33.
Manley, R. St J. & Mason, S. G. I952 J. Colloid Sci. 7, 354.
Manley, R. St J. & Mason, S. G. I954 Canad. J. Chem. 32, 762.
Mason, S. G. & Manley, R. St. J. 1956 Proc. Roy. Soc. A 238, 117.
McDowell, C. M. & Usher, F. L. 1931 Proc. Roy. Soc. A 131, 564.
Meredith, R. 1958 Rheology, theory and applications, vol. ii, p. 300. (Ed., F. R. Eirich.)
New York: Academic Press.
Mooney, M. I95I J. Colloid Sci. 6, 96.
Mooney, M. 1957 J. Colloid Sci. 12, 575.
Nawab, M. A. & Mason, S. G. 1958 Trans. Faraday Soc. 54, 1712.
Oldroyd, J. G. 1956 Rheology, theory and applications, vol. i, p. 663. (Ed., F. R. Eirich.)
New York: Academic Press.
Richardson, E. G. & Tyler, E. 1933 Proc. Phys. Soc. 45, 142.
Smoluchowski, M. von I9I6 Phys. Z. 17, 557, 583.
Smoluchowski, M. von I9I7 Z. Phys. Chem. 92, 129.
Thornton, S. I953 Proc. Phys. Soc. B 66, 115.
Thornton, S. & Rae, D. 1953 Proc. Phys. Soc. B 66, 120.
Vand, V. 1948 J. Phys. Colloid Chem. 52, 277.
Weltmann, R. N. I943 J. Appl. Phys. 14, 343.

LIST OF SYMBOLS
Al, A2 test fluids
B test fluid
C orbit constant
D test fluid
E proportionality constant
F, drag force in particle-mobility approximation

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
22 E. W. Billington

Fe drag force at instant of impact

FL(t) tension in bond at time t
H height of inner cylinder of coaxial cylinder viscometer
Ie, total impulse from bond
I* moment of inertia of inner cylinder of coaxial cylinder viscometer
Ix component of total impulse Ie in direction of flow
K absolute reaction rate
Lo originallength of link
Ao restoring couple per unit angular displacement of the inner cylinderof the
coaxial cylinder viscometer
Me, Me, = Se!2/1r
MT moment of forces exerted on single sphere by the translational motion of
the surroundingliquid
Ns total number of individual spheres per unit volume
No =
No El/Apio
NL total number of links in a bond
Qs, Qe net rate of generation and decay, respectively, of n-type species
R(1, $) orientation factor
velocity gradient
S*(t) flow rate at some time t of shearing as measured at the wall of the inner
cylinder of the coaxial cylinder viscometer
Se velocity gradient at which thixotropic effects are first detected
T absolute temperature
U, V, W components of velocity
U1 U1= oSR(O,q )
X, Y, Z cartesian coordinates

b proportionality constant
c concentration
fL(t) tension in a single link at time t
g(00, S00)distribution function
hi )iS*(t)= hi(oo-(a)*(t))
jz moment of inertia of single sphere
k Boltzmann constant
I semi-majoraxis of ellipsoid
ns, nee density of spheres and ellipsoids respectively
p shear stress
p*(t) shear stress measured at wall of inner cylinder of coaxial cylinder
viscometer
Pt, pt = S
Pe Goodeve stress-unsaturated bond (O< S < i<j
Pa Goodeve stress-saturated bond (S > Aa)
POC flow parameter
qs collision frequency per sphere due to shear

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions
 Flow properties of two types of non-Newtonianfluid 23
qB collision frequency per sphere-Brownian motion
ri, r0 radii of inner and outer cylinders respectively of coaxial cylinder visco-
meter
t time of shearing
t' time of rotation of ellipsoid
tb time at which thixotropic effects first detected in transient measurements
te time associated with extension of a link
,i rate of generation of impulses per unit area
y axis ratio of rigid ellipsoid
8L(t) 8L(t) = L-Lo
e strain
e rate of strain
y viscosity
Yb viscosity of continuous medium
Ys' Ye Y =Ys + Ye-unsaturated bond
,
Ya Y= + Ya-saturated bond
vc effective viscosity of continuous medium
Oi(t) deflexion of inner cylinder of coaxial cylinder viscometer
O3M maximum displacement of inner cylinder of coaxial cylinder viscometer,
for transient measurements using fluids which exhibit thixotropic flow
behaviour
K K=TLS
A flow parameter
AcnAe flow parameters
,Al effective mobility of ellipsoid
sh
IJ0
1-Ue, t = Io( I + AS~)
Itr rotational mobility
6 instrument factor for coaxial cylinder viscometer
GI diameter of individual sphere
'ye, radius of equivalent sphere for ellipsoid mobility approximation
TL lifetime of a single link
Tc period for which an ellipsoid is under compression
Te lifetime of an ellipsoid
TS lifetime of a singlet
Tm,wT time constants characterizing motion of inner cylinder
x extension of a link at rupture of bond
?fs, 3lfe constants appearing in equation for viscosity of a suspension of spheres and
ellipsoids
O)i angular velocity of inner cylinder of coaxial cylinder viscometer
(00 angular velocity of outer cylinder of coaxial cylinder viscometer
Qz angular velocity of a sphere about Z-axis
(r, 0, 54) spherical polar coordinates

This content downloaded from 105.109.103.69 on Fri, 30 Oct 2015 16:38:37 UTC
All use subject to JSTOR Terms and Conditions