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The rheology of clay

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1941 J. Sci. Instrum. 18 159

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 JOURNAL OF SCIENTIFIC INSTRUMENTS
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VOL. 18 A U G U S T 1941 No. 8

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THE RHEOLOGY OF CLAY. BY H. H. MACEY, M.Sc., F.INsT.P.

T h e British Refractories Research Association, T h e Melior Laboratories, Stoke-on-Trent

[MS.receiwed 15th January r g q ]

,US‘XACT’. The rheology of clay-water mixtures, both ‘springiness ’; it shows neither slow elastic after-
liquid and solid, is critically reviewed. Certain discrepancies recovery nor slow viscous deformation. I~ does not, in
between different experimental and mathematical treatments the condition in which it is usually worked, stick to the
of the liquid suspensions are pointed out. The probable
structure of the solid mixtures and their exceptional pro- fingersp a1though tw0 ‘Warate pieces may be united
perties are discussed and it is shown how these properties under Pressure. All these ProPefiies, both Positive and
may be explained by the supposition that the surfaces of the negative, are associated with plasticity. The difficulty of
clay particles repel one another, and thereby appear to be making a join and the tendency for the join to remain
separated by water films. as a plane of potential weakness increases as the
INTRODUCTION plasticity decreases.
THEability of clay to be moulded and to retain a shape
on drying and firing is, of course, one of the fundamental
features of the clay and refractories industry. The im-
portance of its rheological properties to the manu-
facturer is obvious enough. Its importance to the user
of refractories lies in the fact that the behaviour in use
and the life of a clay article are influenced by the
method of making and drying. I t is, for example,
commonly said that clay possesses a ‘memory’, one of
the classical examples of which is to be fpund in a very
simple experiment. If a bar, while in the plastic con-
dition, be bent and straightened, it will, after drying
and firing, be found to have a curvature in the same
sense as that originally given. Simiiarly, articles thrown
on the potter’s wheel tend to ‘untwist’ themselves
during firing. A certain form of failure in s a g g a d , that
of ‘bottom cracking’, has been traced to plastic de-
formation due to stresses set u p during and by the
drying operation. Examples might be cited where the
plastic properties of a clay have been altered by treat-
ment with the object of eliminating a certain fault, but
the life of the article has been shortened by attendant
changes in other properties, Cases are known where
attempts have been made to substitute a clay with more
desirable qualities, e.g. higher. refractoriness, for one
already in use, only to find that either the article could
not be made with the same plant, or failed in use from
other causes, e.g. laminations (Fig. I), due to its
different rheological properties. Fig. I. Example of bad laminations in a wire-cut
Plasticity, the property of being mouldable, is an building brick
intimate combination of several factors. A plastic clay,
mixed with water in suitable proportion, possesses sukh The experimental methods which have been used in
strength or yield value that it does not collapse under attempts to evaluate the plasticity of solid clay-water
its own weight, b u t yet flows readily and without mixtures and to devise a ‘ plasticity number’, show an
cracking in the moulding process. T h e high yield value astonishing diversity. Rods, cones, disks, etc. have
is not to be associated with a high viscosity of the liquid been forced into clay and measurements made of the
as, for example, in bitumens, and is not greatly affected force required; weights have been dropped on test-
by temperature changes, for clay articles are commonly pieces from different heights; clay has been forced
placed directly on to drying floors which have tem- through orifices; in fact, it would seem that nearly
peratures in excess of 70” C . , Clay has, very markedly, every type of mechanical deformation has .been
the property of ‘staying put’, a complete lack of attempted at some time or another. I t is a matter for
___- regret that the labour expended in this way has not
Refractory boxes or containera used to hold pottery greatly extended our knowledge of the subject. It is,
during firing. for example, difficult to correlate the work of Hind
J. S. I. 8
I 60 H. H.MACEY
(I930), who loaded notched tensile test-pieces at a moisture content over the whole range. T h e two
constant rate and obtained a smooth parabolic relation branches are, however, distinct, there being between
between extension and time, with, say, that of Acker- them a range of moisture content where the mixture is
mann (1923)on the penetration of square pyramids into too stiff to pour and too soft for manufacturing pur.
clay, where the length of the side of the depression was poses, which constitutes a sort of unexplored ‘no-man’s
found to be proportional to the cube root of the work land ’.
done, or even with the more fundamentally simple work Two points in the moisture content range are
of Norton (1938) discussed below. I n most of the generally recognized. T h e first of these, which is vague
methods used the systems of shear are of too compli- in its nature, is the moisture content just below that at
cated a nature to be understood and compared. which the material sticks to the fingers, and is known
as ‘best working consistency’. This corresponds to a
THECLAY IIINER4LS hardness such that a moderately sized shape is readily
T h e X-ray structure of the various hydrated alumin- mouldable, but yet will not deform under its own
ium silicates which constitute the clay minerals is now weight-a natural and fortunate coincidence. With de-
fairly well established (review by Kerr, 1938). These crease in moisture content the material hardens and
are divisible into three main groups, distinguished by shrinks, the change in volume being equal to the
structure, dehydration and thermal characteristics and volume of water lost, until the shrinkage ceases with
base exchange capacity rather than by chemical com- comparative suddenness. T h e moisture content at
position. T h e groups comprise (U) the kaolinite, in- which this occurs corresponds to the condition k n o w
cluding nacrite, dickite and halloysite, (b) the serecite- as ‘leather-hard’ ; it varies from clay to clay, generally
illite group, and (c) the montmorillonite, beidellite and lying within the range of 8 to 12 per cent on the dry
nontronite group. They all have a sheet structure, that weight. This point, which can be easily evaluated with
of illite being closest to the micas, and may be built up reasonable accuracy, is of importance, since below it the
of layers of aluminium and oxygen and of silicon and material is not plastic, even under considerable pressure.
oxygen. The kaolinite sheet is composed of one of each T h e change in volume between leather-hard and com-
of these layers, the whole being built up of such plete dryness, which may be either positive or negative,
sheets separated by a gap of a few- Angstroms. T h e is very small and is usually neglected. In the leather-
montmorillonite sheet has an alumina layer bounded on hard condition the clay is a hard solid which can be
both sides by silica layers. Here the bond between the polished with the finger nail and possesses its maximum
sheets is weaker and X-ray diagrams suggest that water resistance to breakage. At lower moisture contents,
will build up in crystalline form and in integral numbers although the tensile or transverse strength increases, the
of layers between them. The number of such layers can clay is more brittle.
be varied by suitable treatment, e.g. they are reduced Moisture content is thus of paramount importance
by heating, the distance between the montmorillonite in considering the behaviour of any particular clay. It
sheets varying accordingly. The interlamellar swelling varies so widely in. different clays that it constitutes
is one of the most interesting features of the silicate one of the greatest difficulties in their comparison. In
structure, and there can be no doubt but that this illustration, a common figure for the moisture content
affinity between water and the silicate surface is re- at best working consistency for a fireclay is 18 to 20 per
sponsible for many of the peculiar properties of plastic cent, and that for a ball clay or certain brick clays might
clay. Various atomic substitutions are possible within be 3j or 40 per cent. In general, a high working
the lattice, which may alter the residual surface charge moisture content is associated with a high moisture
and modify the properties of the mineral. Free silica content at the leather-hard condition, though this is by
or alumina may be present in clays although kaolinite no means a definite rule. This tendency is responsible
,is generally the most common constituent. for the unsuccessful attempts to evaluate plasticity by
From the commercial point of view, clays are classi- ‘shrinkage water’ or ‘water of plasticity’, the difference
fied according to their uses. Thus we have the fireclays, . in moisture content between two arbitrarily chosen
which may be either siliceous or aluminous according consistencies. Nor will two clays have comparable
to their chemical composition, the latter being usually consistencies throughout the range if their moisture
of finer grain size and more plastic; the brick clays, contents bear a constant ratio. T h e properties of the
closely related to the fireclays, but of lower refractori- mixtures do not run parallel on different scales.
ness due usually to a higher iron content; the ball clays,
renowned for high plasticity; the china clays, of low THESTRUCTURE OF THE PLASTIC MIXTURE
plasticity, and many others. T h e range is a wide one and T h e shrinkage behaviour led Mellor to suppose that
includes minerals with very diverse characteristics, some the clay particles are separated by water films which
being sandy and others distinctly greasy to the touch. decrease in thickness as the drying proceeds, shrinkage
ceasing when the particles come into contact. This
MOISTURE CONTENT
theory of structure has been almost universally adopted
Rheologically, the study of clay-water mixtures is by those associated with the clay industry (Norton,
naturally divided into that of the ‘slips’ or liquid sus- 1933). More recently, the idea of a water film, W7hlCh
pensions and that of the solid plastic ‘bodies ’ 8 ,although, implies a binding of the liquid to the solid surface, has
of course, their properties must vary continuously with been replaced by the slightly different view that the
separation of The surfaces is due to a repulsion benveen
* The term ‘body’ is generally applied to a plastic mass them (Houwink, 1937). The theoretical aspects m-
into which two or more clays or other ingredients have been volved have been worked out independently by
blended. It is here used in a wider sense, to include also Freundlich (1935)and Hamaker (1936). Over a large
single clays in plastic condition. range of separation, from very small distances upwards)
 T H E RHEOL(3GY O F CL.4Y
the preponderant force is a repulsion of a form similar
to that of Debye for the potential drop IJ from a surface
#=(Ke-*”)/x,where K and b are constants and x is the
distance from the surface. The variation of this ex-
pression is mainly determined by the exponential
term.
The repulsion between the particle surfaces may be
estimated by a determination of the equilibrium moisture
contents when the mixture is compressed under con-
stant load between porous pistons. An exponential
relation is found between the applied pressure P and
the moisture content M of the form P = Ze-PJ”, where
2 and p are constants peculiar to each clay or, more
strictly, to each batch of clay. T h e distance of se-
paration of the particles being small compared with
their average size, the moisture content is approxi-
mately a linear function of the distance of separation, x,
and the parallel with Debye’s expression is complete.
In order to account for observed rates of flow of water
through plastic clay, the author (1940)has put forward
the supposition that there exists, in the water near the
clay surface, a tendency towards regular arrangement or
a probability of structure. The properties of montmoril-
lonite indicate that a layer of water in crystalline form
is to be found immediately at the silicate surface. Here
the probability of structure is unity, and a skeleton
lattice is imagined, in continuation, extending outwards
from that surface. T h e probability of structure is that
of finding an atom at a lattice point and decreases with
distance from the surface. Normal thermal agitation
exists but paths pass with greater frequency through
these lattice points. T h e rate of destruction of this pro-
bability of structure with distance from the surface, by
thermal agitation and the presence of ions, may reason-
ably be expected to be proportional to its value at any
point, from which the exponential relation follows. Two
such systems, based on opposing surfaces, necessitate
mutual destruction at the mid-way point and energy
will be required to bring the surfaces closer together.
This appears as a repulsion between the surfaces, in-
creasing as the separation decreases. Once two surfaces
have been brought to a specified distance apart, how-
ever, it does not follow that the process is immediately
reversible. Experiments between porous pistons in
which the load is removed after equilibrium has been
attained have shown that there is a very large hysteresis.
It is also known that long times are required to even out
moisture contents by storage.
The rigidity of the plastic body is due to this net-
vvork of repulsive forces. T h e increase in the magnitude
of the forces with decrease in moisture content results
in the well-known hardening. On application of shear,
the particles slide over one another, but on its removal,
a similar force system remains, and the material IS
capable of retaining its deformed shape.
The alternative theory of structure is that of Terzaghi
(I927), and arose from certain similarities of shape
between the pressure/moisture content curves of clay
and those of mixtures of sand and mica. It states that
the clay particles are in contact at certain points, and
build up into a honeycomb or interlocking series of
bridges, formed by the smaller particles between the
larger. No critical experiment has yet been devised on
which a decision between these tu-o quite dissimilar
theories can be made. At present, preference for either
theory is largely a matter of personal opinion, which is
161
bound to be influenced by familiarity with particular
aspects of the subject.
T h e major objection to the surface repulsion theory
is the large distances over which it is necessary that the
repulsion shall act, up to some 103A. For a discussion
of the theoretical possibility of this, reference may be
made to Houwink (1937). It must be emphasized that
the repulsion does not involve completely bound water
films of this thickness. T h e supposition of a probability
of structure also avoids a sudden transition, within
molecular distances, from bound water at the surface
to perfectly free liquid. The similarity of pressure,’
moisture content curves found by Terzaghi for clay
and sand-mica mixtures was only one of shape, the
moisture content ranges being quite different. T h e ratio
of voids in a honeycomb structure does not depend on
the scale of that structure, so that this difference is
difficult to explain. So also is the increase in moisture
content at similar consistency with decrease in grain
size, either in different clays or produced in the same
clay by grinding. Another objection to this theory is
the fact that the exponential relation between applied
pressure and moisture content has been found to hold
reasonably well for all clays so far known to have been
tested. This would not be expected to be the case if
the relation were due to the successive collapse of
bridges of varying strength composed, in different clays,
of particles of widely different grain size distribution.
The greatest objection, however, arises from the fact
that the cleavage of kaolinite, the major constituent, is
not great. Considerations of the small concentrations
at which evidences of structure are seen ( j per cent of
some clays) necessitate more than one particle in a con-
necting link or bridge. For the rigidity of the whole, the
bridge must be stable in compression as well as in
tension, and the linkage between the particles must
therefore be rigid. The plastic mixture is obtained by
violent mechanical mixing of the two constituents. I t is
difficult to imagine inter-particle forces of sufficient
complexity to be responsible for the original setting u p
of the bridges under these conditions, or their rapid
collapse and reformation during plastic deformation.
Such forces would need be of very high attraction a t
certain spots on the particle surface, combined with
repulsion between other parts of the particles acting
over much greater distances than 103 A.
LIQUIDSLIPS
The use of some form of simple viscometer as the
experimental method with liquid slips is obvious. De-
formations being thus simple in shear, the under-
standing of the rheology of slips is rather more advanced
than that of the solids, although both have received
roughly the same amount of attention. Bingham’s treat-
ment (1922)was, perhaps, the first step in the elucida-
tion of the problem. He plotted rate of flow through
capillary tubes against stress, a procedure which will
give a straight line passing through the origin for a true
liquid, the slope of which is a measure of the viscosity.
Straight lines were also drawn through the experimental
results for suspensions, and were extrapolated down-
wards to cut the stress axis at a positive ‘ yield value ’.
This was subtracted from the actual applied stress in
calculating the slope of the line, or the ‘mobiliq’’.
Actual experimental results at low values of stress give
a curve falling off tangentially to the stress axis, flow
8-2
 I 62 H.H.MACEY
being observed at values of the stress below the Bing-
ham ‘yield value’. Houwink’s suggestion that the point
at which flow is first observed should be called the
‘lower yield value’ does not seem to have been generally
accepted. Ostwald (1925-37)preferred to consider the
relation between rate of flow- and stress a parabolic one.
Either interpretation of the experimental results is
equally possible, according as more emphasis is placed
on the upper or the lower portion of the curve.
Bingham’s treatment fails if flow through capillaries
of different sizes be compared. Lack of recognition of
this fact has led to the occasional publication of peculiar
results. Thus, for example, Irwin and Bevis (1938)
devised a very simple viscometer consisting of two
capillaries, of different lengths and diameters, fed from
a common reservoir. Measurement of the rate of flow
through each of these is made simultaneously and two
points obtained of rate of flow against shear through
which a straight line is drawn. Frost and Hunt (1939)
have made measurements (which they emphasize are of
a comparative nature) on enamel slips with this in-
strument, and a large proportion of their lines cut the
flow axis at positive values.
At certain consistencies and stresses, a clay suspension
may flow through a capillary tube as a solid core, shear
taking place only in those regions adjacent to the walls
of the capillary. The names of Buckingham (1921)and
Reiner (1926)are independently associated with the
mathematical analysis of this type of flow. A more
complete treatment of the whole problem is that of
Scott-Blair and his co-workers. Schofield and Scott-
Blair (1930-5)have deduced a general equation which
can be reduced by integration and supposition of the
requisite conditions to the various expressions for the
different forms of flow which have been put fonvard.
Dix and Scott-Blair (1940)assume that the streamlining
layers are not infinitely thin so that a summation treat-
ment takes the place of integration. The conditions that
there is a dynamic friction between the layers and also
a static friction requiring an initial shearing stress
produces the Buckingham-Reiner equation. Simple
dynamic friction and infinitely thin layers result in
Poiseuille’s form. T h e plug flow of Buckingham is given
by the extreme case where the thickness of the layer
is equal to that of the capillary. It is also claimed that
this treatment will account for what has been called
the ‘sigma’ phenomenon. This is concemed with flow
through capillaries of different radii. The flow through
a small capillary is greater than would be expected from
measurements of flow through a larger, i.e. the smaller
the tube, the greater is the apparent mobility. Scott-
Blair argues (1938)that the suggestion of Ambrose and
Loomis (1934)that this effect is due to thixotropy is
untrue, since Schofield and he found that an increased
length of tube produces no anomalous effect and the
amount of shear is here increased without affecting the
consistency. One of his basic assumptions, however,
is that the velocity gradient at any point is some function
of the shearing stress at that point. T h e conception
thereby implies that the material quickly settles down
to a steady state which is maintained throughout the
length of the tube. If thixotropy be associated with the
rate of shear, rather than the amount (in time), it is
not to be expected that the effect of the length of the
tube should be anomalous, and Scott-Blair’s dissocia-
tion of the ‘sigma’ phenomenon from thixotropy is not
necessarily true. T h e argument is one of degree rather
than of kind, for if the material (other than clay, e.g.
cream) be such that the thixotropic breakdown takes
place slowly and progressively, the rate of flow through
a long tube will be relatively greater than through a
short. In other words, the finding of Scholfield and
Scott-Blair might be due solely to their use of tubes
which were of ample length for their particular
material.
Richardson (1933) investigated, with a hot-wire
anemometer, the distribution of velocity between the
cylinders of a Couette viscometer and gives, (1938)
amongst others, a family of four experimental curves of
this nature. T h e radii of the cylinders were 6 mm. and
12mm. respectively, the outer rotating, and the curve
at the lowest velocity ( j ’ j cm./sec.) shows shear only
over the millimetre adjacent to the inner cylinder. The
angular velocity is constant throughout the other 5 m.
of slip. This corresponds to the plug flow of Bucking-
ham. At a velocity of 8.5 cm.,/sec., the shearing takes
place over about 2 mm., the solid plug being reduced
to 4 mm. in thickness. At a velocity of 12cm./sec., the
shearing layers are increased to about 3 mm. and at
16cm./sec. to about 4 . j mm. This variation in the
thickness over which shear takes place apparently
invalidates Buckingham’s equation, which is based on
the very simple postulate that the friction is due to the
shearing of a thin film of assumed fluidity and thick-
ness. I t also shows that the rate of shear, considered as
the relative velocity of two parallel surfaces divided by
the distance of separation, has no physical significance
in the flow of clay slips. Most especially it indicates
that the overall relations between flow and stress in any
type of viscometer are governed by the behaviour of a
very small proportion of the material, particularly that
at points immediately adjacent to the solid plug. Here
the rate of shear is very small, so that it would seem
that any intimate understanding of the problem is to
be achieved by studies of flow at very small rates of
shear, and not by placing the emphasis on the high
rates as is the tendency in the treatments of Bingham
and of Scott-Blair and his collaborators.
Other curves of velocity distribution due to Richard-
son do not shom true plug flow, the angular velocity
increasing continuously between the inner and outer
cylinders, and the velocity gradient increasing with the
speed of the outer cylinder. T h e curves, however,
differ from that for a true liquid in that the velocity
gradients are very high within the millimetre adjacent
to the inner cylinder. This residual plug flow indicates
that the flow of these suspensions might be considered
as a combination of the various types of flow, the pro-
portion of each varying with the concentration. Plug
flow, for example, will not come into being suddenly
and irrevocably at some arbitrary concentration, but
the tendency towards it will increase as the concen-
tration of the slip increases. There appears to be a need
for some experiments with greater emphasis on concen-
tration and the effects of its variation.
Additions of alkalies are commonly made to the
casting slips used in the pottery industry to increase
fluidity and permit the use of higher concentrations.
Sufficient has already been said to indicate that it is
extremely unlikely that this increased mobility is a
simple shift of the moisture content scale, and much of
this effect still remains but little understood.
 T H E RHEOL(3GY O F
SOLID‘BODIES ’
With the solid mixtures, the experiments most
simple in shear are those of Norton (1938), who
describes a n apparatus by which torsion tests on
hollow clay cylinders may be conducted. Practical
difficulties in such a method lie in the holding of the
ends and the restriction of the upper moisture content
limit by the necessity for a test-piece of such strength
that it will not deform under its own weight when
supported only at the two ends. T h e material, when
distorted, shear hardens, and Norton uses three pro-
perties to express the ‘workability’ of a clay. These
are the ‘yield point’, shown in his stress-strain diagrams
as a sharp break from an initial straight line; ‘the
maximum strength’; and the total deformation at the
breaking point, ‘the ductility’. He obtains a curve with
a sharp maximum by the multiplication of the yield
point by the maximum deformation, and considers that
this usually occurs at the condition of best workability.
400 v body is due to a repulsion between opposing particle
d regions correspond, on a much larger scale, to the
:. 200
2 for the plasticity of single metal crystals. T h e parallel
8 is not, however, a complete one, for in the crystal most
h of the atoms are in positions of minimum potential
100
10 20
Angle in degrees
Fig. 2. Initial portions of torsional stress-strain curves at
different speeds (after Norton)
He also considers the initial straight line of the stress-
strain curve to be elastic, but publishes a family of such
curves obtained (apparently on test pieces of the same
moisture content) which show that the ‘yield point’
decreases as the speed of rotation of the apparatus
decreases (Fig. 2). At the same time the slope of the
straight line, or the elastic modulus increases. T h e
Curves indicate that this latter tends to infinity when
the rate of distortion is very small, while at the same
t h e the ‘yield point’ disappears. Norton also describes
an experiment in which the apparatus is stopped after
a series of increments of mist. On each stopping the
clay continues to yield under the tension of the springs
used to measure the torque, but ceases to do so each
t h e when the torque has reached roughly the same
value. This value is approximately equal to that of the
break in the initial deformation line, the ‘yield point ’.
Sorton argues that this behaviour shows that the clay
is truly elastic below this yield point, but since this is
affectedby the speed of the experiment, the agreement
must be accidental. There appears to be confusion here
CLAY 163
bemeen a break in the stress-strain curve, the reason
for which is obscure, and the yield point in the sense of
that stress below which no continuous flow takes place.
I n tensile experiments, e.g. those of Hind ( I ~ o ) or ,
those of the author (Fig. 3), smooth stress-strain curves,
with no sign of a break, are obtained.
It was noted some time ago (Zschokke, 1906 ; Salve-
tat, rgzo), that the degree of extension before failure of
a tensile test-piece, the ductility, increases considerably
as the speed of extension or the rate of loading is
increased. I n this respect clay differs from almost
every other known substance, the only mention of
similar behaviour being in some experiments by Mait-
Land (1886) on steel, where the ductility was found to
increase some three times when the fracture was caused
by the explosion of gun-cotton. This property demands
a high degree of skill from a moulder, who must pro-
duce his deformations quickly in order to keep the
shear hardening a minimum.
It has been assumed that the rigidity of the plastic
surfaces. An arrangement of particles of different sizes
might be imagined in which these repulsive forces were
everywhere the same, the distance of separation being
uniform, but such perfection of packing is not to be
found in ordinary clays. It is therefore to be expected
that regions exist in which the forces, though in a state
of equilibrium, are not even, and the particles are not
in their positions of minimum potential energy. Such
‘dislocations ’ which have been suggested to account
energy. In the clay the ‘perfection of packing’ and the
potential energy will vary arbitrarily throughout the
mass u p to the maximum value possible without sliding
m d rearrangement.
When a stress is applied to such a system, slip planes
will be set up through the regions of highest potential
energy, and the material will be plastically deformed.
But, as shearing proceeds, new arrangements of
particles will be found and it is probable that some of
these will be sufficiently stable to cause the slip plane
to seize. The clay will, in consequence, shear harden,
and as the stress increases new slip planes will be
brought into being through areas previously stable. The
number of such new planes will increase as the force
approaches that necessary to deform a system of perfect
packing, and at the same time the probability of seizing
will decrease. Thus the rate of shear hardening will
decrease as the extension proceeds. Such a mechanism
has been found capable of explaining the shape of the
stress-strain curves for tensile specimens.
Rearrangement of particles implies that there shall
be a reduction in distance of separation at certain points
and an increase in others. Since the increase will only
take place slowly, time must be expected to have a large
effect in plastic behakiour. If the rate of deformation is
small, the particles will have time to readjust them-
selves without initiating slip planes, and the total de-
formation before failure will be small. If the speed of
deformation be great, not only will the slip planes come
into being, but there will be less chance of finding more
stable arrangements. The rate of shear hardening will
be small and the ductility great.
 164 H.H.
If a small force be applied to such a system as this
for a long time, the stress will be accommodated both
by distortion of the force network and slow rearrange-
ment of the particles. O n the removal of the force,
only the deformation due to the distortion of the force
network is recoverable. T h e material has no Young’s
IModulus, i.e. elastic range, and zero yield point in the
sense of that stress which will produce a permanent
plastic deformation. This has been verified experi-
mentally (Macey, Keeling and Booth, 1939).
Under a small force, then, such as its own weight, clay
deforms plastically until it has shear hardened suffi-
ciently to resist further distortion. In most cases this
deformation is small, about one-hundredth of the total
possible, and is neglected. Where the clay is soft, how-
ever, or the manufactured article is large, this ‘slump-
ing’ may be appreciable, and such articles are removed
from the drying floor at a suitable stage and trimmed to
more accurate shape. The degree of such slumping is
influenced by the care with which the article is placed
on the floor, but does not increase with time. I t is not
to be confused with slow viscous deformation such as
occurs with pitch.
-4s the stress is increased a value is reached when the
rate of shear hardening is insufficient and continuous
flow- and failure takes place. T h e clay has a yield value
in this sense, but one which is extremely difficult to
measure as it will be affected by the rate of application
of the load. For the same reasons the maximum strength
show-n by a tensile test-piece will increase as the rate of
deformation is increased.
When the solid mixture is extruded, e.g. through the
die mouth of a pug, relative movement between portions
of the column produces shear hardening. In extreme
cases the whole of the shear thus becomes concentrated
in a very few planes, which persist during drying and
firing as planes of weakness running through the article.
It would, for example, be quite easy to peel off from the
brick illustrated in Fig. I its outer portions, leaving an
elliptical core. T h e indication is that experimental
methods involving considerable or continued shear are
to be avoided, for even if the concentration of the shear
into a very limited thickness is recognized, the pro-
perties of the material there are not the same as through-
out the bulk.
T h e major requirement for high plasticity may be
said to be a slow shear hardening at some suitable
working consistency or strength. T h e probability of
seizing of the slip planes must be small, so that, in
general terms, plasticity is dependent on the perfection
of packing of the particles. This is a matter primarily
of size distribution, but if numbers of.large particles are
present, the size distribution for good packing is more
critical. Thus the harder and larger grained clays tend
to be less plastic. If it be assumed that, at best working
consistency in different clays, the similarity of hardness
is due to a similarity in the value of the inter-surface
repulsion, the asso-iation of small average grain size
with high working moisture contents may be explained.
That this is, however, no criterion of plasticity is shown
by the china clays. These have a fairly uniform grain
size of intermediate dimensions, and high moisture
contents, but are poorly plastic because the finest
fractions are removed during the sedimentation which
is part of the ‘getting ’ process, and the packing is con-
sequently poor.
More intimate comparison of different clays on this
MACEY
basis proves to be more difficult. They may not, as
already indicated, be compared at the same moisture
content. If ductilities at the same maximum strength
be taken, the speed at which the experiments are con.
ducted has a large influence. T h e ratio of the ductilities
will vary at different speeds, and may possibly be re-
versed.
So far no mention has been made of the shape of
the particles. These are flat, but not excessively so, and
will be orientated by working into the plane of the
shear. I n the barrel of a pug, where the clay is forced
forward by rotating pitched knives, the particles are
orientated with their larger dimensions at right angles
to the axis of the pug. In subsequent drying, the linear
shrinkage in this plane is less than in the direction of
the axis of the pug. Experimental comparisons of these
shrinkages (Macey and Wilde, 1939) show them to be in
the ratio of about 6 to 7 . If the orientation were com-
plete and the distance of separation equal on all sides of
the particle, this would also be the average ratio of the
two axes of the particles. T h e lack of symmetry must,
of course, be greater than this, but it does not seem
likely that it will greatly exceed about z : I.
GO1 I
IM I
0
0 10 20 30
I
40
EXTEIVSION i % l
Reproduced by permission from Bulletin ofthe
British Refractories Researcii Association
Fig. 3 . Tensile stress-extension curves of bars of the same
clay of almost identical moisture content, produced under
identical conditions, showing typical lack of agreement
between ‘repeats ’
Many of the ‘memory’ effects of clay are due to
orientation of particles, while, rheologically, shear in
a plane of orientation will not be the same as in one at
right angles. T h e orientation in a specimen is influenced
by the method of making and probably the history of
the clay prior to this. I n addition, phenomena of stress
and strain are based on the probability of the behaviour
of a system which is of comparatively coarse structure,
where the number of slip planes involved is few. These
two factors, in conjunction, result in a serious lack of
reproducibility in experimental results, deviations of 30
or 40 per cent from the mean being.common. .An
example of the type of deviation encountered is shown
in Fig. 3 (Macey, Keeling and Booth, 1939). These
stress-strain curves were obtained in tensile experi-
ments in which the rate of extension was constant. The
bars to which the curves refer were cut off from the
same extruded column, while the experimental con-
ditions were identical in every way. Experimental
technique is further complicated by the rapid variati0.n
of properties with moisture content and the impossi-
bility of making a number of test-pieces identical in this
respect. There are, for example, differences in moisture
 T H E RHEOLOGY OF CLAY
content between the centre and edges of a column of
clay issuing from a pug. These are ignored com-
mercially, but may be appreciable in the laboratory. T o
add to these difficulties, two batches of plastic clay pre-
pared from the same original supply by the same
method may differ considerably. Keither can a large
batch be made, for the mixture matures on storage and
its propertfes alter.
An interesting phenomenon, which is only exhibited
by certain clays, is that of ‘backlash’ (Macey, 1941).
This is very readily recognizable by feel, but no
attempts at measurement have yet been made. If a
portion of the clay be held between the fingers and
thumbs of both hands and alternately pulled and
compressed, a range of easy movement is felt, cul-
minating in a sudden resistance at each end of the cycle.
The effect becomes much more pronounced as the
rapidity of the cycles is increased, while with some
bodies the treatment produces beautifully defined series
of slip planes on the surface of the clay. T h e clays
which behave in this manner are those which have
been produced commercially by a sedimentation pro-
cess, e.g. the china clays and an exceptional fireclay
which is settled out from the washings of another
refractory material. T h e phenomenon ,can be attributed
to the shape and packing of the particles. Sedimenta-
tion removes the finest fractions of particle size, and
thereby allows the flat particles to slide relative to one
another under quite small stress. An associated obser-
vation is that the ‘aqueous conductivity’ of these clays
-the rate at which water will flow through them under
comparable conditions-is about one hundred times
that normally found, due to this same poor packing or
open structure.
Although clay shear hardens on deformation, it is,
at the same time, thixctropic. Like ‘backlash’, this fact
is not generally recognized, for all recorded experiments
seem to be of the single stress to failure type in which
thixotropy mould not be apparent. Kevertheless, it
cannot be ignored commercially. Before the actual
moulding of an article on the potter’s wheel, a thrower
causes his clay to rise and fall a few times between his
hands, softening it and producing a better condition
for the moulding process. T h e amount of thixotropy
increases with the proportion of ball clay in a com-
pound body, while if bentonite be present, the softening
is so marked that the mixture is apt to be unmanageable.
It would seem that during a violent working, neigh-
bouring particles are forced closer together, but, as
already explained, they do not separate again im-
metiiately. There will, as a result, be vague conglo-
merations of slightly lower moisture content in a matrix
or atmosphere of slightly higher moisture content, the
greater fluidity of which (lower repulsive forces) pro-
duces a softening of the whole. T h e mixture hardens
again on standing as these irregularities disappear. If
the body contains a fair proportion of very small
particles, the packing of these conglomerates will be
good and their resistance to shear and breakdown large,
i.e. the ball clays and the bentonites show appreciable
thixotropy. If no small particles are present, poor
packing will decrease both the tendency to formation of
these semi-stable conglomerates and their strength. T h e
thixotropy of a slip may be similarly explained, except
that in cases of simple plane shear, the conglomerates
%dlbe two- rather than three-dimensional.
ivhile, then, we have a reasonable working hypo-
16j
thesis, and grain size distribution appears to be the
major factor in plastic behaviour, much remains to be
understood before these different facets of the subject
can be correlated, or the properties of a clay varied at
will on an industrial scale. There is the problem, at
present unsolved, of measuring ‘packing’, a combina-
tion of size distribution and particle shape. More im-
mediately, the two branches of study, the solids and the
liquids, need to be brought more closely together by a
more thorough exploration of the ‘no man’s land’ which
lies between them, and a consideration of apparently
irrelevant data, such as shrinkage behaviour and the
pressure/moisture-content relations of clays investi-
gated in the slip form. At the moment, the only links
seem to be the possibility that plug flow might be a
form of shear hardening, and the persistence of some
degree of thixotropy throughout the whole range.
ACKSOWLEDGEMEKT
I am indebted to the Council and Director of the
Association for their permission to publish this article.
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