JOURNAL OF MATERIALS SCIENCE 29 ( 1 9 9 4 ) 1 3 7 4 - 1 3 8 1

Rheological behaviour of fresh cement paste

as measured by squeeze flow

B. H. M I N * , L. E R W I N * , H. M. J E N N I N G S t
Departments of Mechanical Engineering* Material Science and Engineering* Civil Engineering t,
Robert R. McCormick School of Engineering and Applied Science, Northwestern University,
Evanston, Illinois 60208, USA

A method is proposed for measuring the rheology of cement paste under conditions that suppress
shear flow, i.e. squeezing. This method is based on squeezing samples in a servohydraulic
compression-tension testing machine, and is different from the commonly used shear flow
experiments. Possible artefacts such as the buoyancy of the piston that penetrates the paste,
sedimentation of cement paste, geometry of the container, and friction at the interface between
the top plate (or piston) and sample are investigated. Plots of stress versus apparent strain were
obtained and compared with results from standard shear flow experiments. Because cement paste
has both viscoelastic and viscoplastic characteristics, results are analysed in terms of both
solid-like deformation and liquid-like flow behaviour. A first-approximation theoretical analysis is
developed, based on the assumption that cement paste behaves as a non-Newtonian liquid, and
results are compared with the experimental results.

Nomenclature CGF Geometric factor for cement paste

Shear strain rate in power law fluid model do Amplitude of squeeze motion
"~'zr Shear strain converted from e=r FN Load in normal direction
"Yzr Shear strain rate 9 Gravitational constant
Normal strain rate h Sample height
I?.zr Component of shear strain ho Initial sample height
8zr Component of shear strain rate /~ Velocity of platen
I~zz Component of normal strain k Order of polynomial function of geometric
q Viscosity factor for cement paste
P Density of cement paste (3.2 g cm- 3) m Consistency in power-law fluid model
(3"Cav Calculated average normal stress of cement n Power index in power-law fluid model
paste P Pressure
(3"Nav Calculated average normal stress of power P, Atmospheric pressure
law fluid PGF Geometric factor for power-law fluid model
~m Measured normal stress of cement paste r Radial direction in cylindrical coordinates
(Yzz Normal stress in z direction R Radius of sample
"l~eq Equivalent shear stress converted from nor- s 1In
mal stress V Volume of the top platen submerged into
T,rz Shear stress in momentum equation cement paste
ai Coefficients in polynomial function of geo- vr Velocity in r direction
metric factor for cement paste v= Velocity in z direction
B Buoyancy force z Vertical direction in cylindrical coordinates

1. I n t r o d u c t i o n age of these simple geometries is the relative ease of

The rheology of cement paste is complex, and flow controlling shear rate and shear stress. Rheological
properties such as the relationship between shear rate properties under shear flow conditions may be good
and viscosity are the subject of ongoing research. indicators of the characteristics of pastes at initial
Viscometric flow conditions are usually obtained us- stages of hydration, even though the specific values are
ing plate-plate, cone-plate and coaxial cylinder vis- functions of sensor geometry and are often complic-
cometers that deform the specimen under simple shear ated by many artefacts. Flow properties incorporate
flow. The flow has been controlled in several ways strain-rate and time-dependent behaviour under large
including constant shear rate [1-5], varying the shear deformations. Typically, results show that cement
rate [6, 7] and oscillatory shear rate [8-10], as well as paste obeys a Bingham type of behaviour. Thus, a con-
controlled stress and creep [11]. The greatest advant- nection may be made to microstructure in that the

1 374 0022-2461 9 1994 Chapman & Hall

flocculated system yields or breaks down in the small- with experimental results. The derivation assumes an
strain region. equibiaxial extensional flow; that is, under the condi-
Although flow under shear stress has been emphas- tion there is no shear stress between the top plate and
ized in the literature, there is another class of flow, the sample surface.
known as shear-free flow, that includes elongation,
squeeze and planar flows, which are important to
processing. Obviously there must be shear planes as- 1.1. Research s i g n i f i c a n c e
sociated with deformation, but these planes, oriented It must be emphasized that the experiments and ana-
45 ~ with respect to the applied normal stress, are not lyses reported in this paper are complex and, as a res-
stable when a specimen is squeezed between two ult, many approximations and simplifications have
platens, i.e. when the distance between plates is chan- been made. For example, because some of the sample
ging. Deformation, therefore, occurs by flow along squeezes out from between the plates the concept of
planes which are constantly being disrupted and re- strain, according to mechanics, cannot be applied.
defined. However, it is useful to approximate an apparent
Other materials which have been studied extens- strain from "the displacement of the platens, particu-
ively using squeeze flow experiments are polymer larly at Small displacements. Here apparent strain is
melts [12, 13], suspensions [14], composites [15, 16J, calculated by integration of strain rate; described by
asphalts [17], coal tar pitch [18] and elastomers the velocity field under squeeze flow. This apparent
[19, 20]. For example, the rheological behaviour of strain is called the Hencky or logarithmic strain [23].
viscoelastic polymers in squeeze flow is very import- Hencky or logarithmic strain will be used on the
ant in order to understand and improve polymer pro- assumption that there is no flowing of the sample over
cessing operations such as film blowing, fibre spin- the top plate and no friction between the plate and the
ning, flat-film extrusion, blow moulding and vacuum sample. Even with this qualification, the results re-
forming. ported in this paper provide a basis for studying the
Squeeze flow conditions occur during the mixing of shear-free flow behaviour of fresh cement paste.
cement paste, mortar and concrete. They are domi-
nant factors when considering processes such as
moulding and extrusion. Also, for concrete or mortar 2. Theoretical analysis of cement
there may be a squeeze behaviour that occurs between paste assuming non-Newtonian
aggregates. With few exceptions [21, 22], squeeze flow fluid behaviour
experiments have not been applied to cement paste Fresh cement paste is not a Newtonian liquid since its
because of the difficulties involved in controlling the viscosity is a function of strain rate. Such a fluid obeys
experiment. Notably, the paste may flow under the a power law, proposed by Ostwald [24] and de Waele
influence of gravity before squeezing, and the problem [25], and follows the functional form
of containment has not been studied. This means the
n(~) = m~ " - 1 (1)
rheological characteristics of cement paste have not
been completely analysed. where m and the dimensionless n are parameters com-
This paper describes squeeze flow experiments that monly called the consistency and power-law index,
can be performed under constant stress or constant respectively. The squeeze flow problem for a power-
strain rate (constant velocity of top plate). Results are law fluid has been solved by Leider and Bird [26].
presented from constant-velocity experiments on ce- Cylindrical coordinates (taking Vr = v,(r, Z), Vz = Vz(Z)
ment paste. In the process of establishing an experi- and p = p(r), and discarding all internal terms) are
mental technique, artefacts such as the buoyancy placed midway between the discs as shown in Fig. 1.
force, sedimentation in cement paste; the effect of the In addition to the assumption of a quasi-steady state,
geometry of the bottom container, and the effect of a condition of no-slip at the interface between paste
friction at the interface between top plate and sample and sensor is invoked. In the light of these simplifying
surface are considered as independent variables. The assumptions, the continuity equation and momentum
last variable is studied under two conditions at the equation reduce to
interface, namely no-slip and slip. In the no-slip case,
1 (~(rvr)) ~Vz
where the boundary layer of paste has zero velocity, 7 ~ + cqz - 0 (2)
squeeze flow is a coupled effect of both shear and
compression. In the case of slip with a non-zero velo-
city condition at the interface, flow occurs along
planes which fold as the distance between the plates
changes. In particular, this case is equivalent to
equibiaxial extensional flow. Results of constant-velo- sensor
city squeeze experiments are compared with those of
our constant-shear experiments [1], after normal
stress and apparent normal strain are converted to an
equivalent shear stress and shear strain under the
assumption of a uniaxial compression test.
no-slip condition
An analytical relationship between average normal
stress and apparent strain is derived and compared Figure ! Geometryof squeeze flowof non-Newtonian fluid.
1375
and factor for cement paste is

Or + ~z = 0 (3)
(14)
~cav = m~" 2"(3 + n ) ~ o a~

From the no-slip condition, the following boundary

conditions are invoked:
3. Experimental procedure
vr = 0 at z = h (4) A typical Type I Portland cement was used, and the
zrz = 0 atz = 0 (5) cement paste was prepared by mixing cement and
water in a Hobart mixer. The water/cement ratio by
and weight was 0.4 for all experiments. Mixing intensity

/)r --
ht+ [ - 1 ( dp 1' 1 z)'+s] (6)
and time of mixing were 30 r.p.m, and 5 min, respect-
ively.
As shown in Fig. 2, the apparatus for measuring
where s = 1/n. The pressure profile is calculated with rheological properties consists of a top plate connec-
the following boundary conditions: p = P at r = r and ted to a load cell and a bottom container. The dia-
P = Pa at r = R. It is expressed by meter of the top plate was 203.2 mm, and the diameter
of the bottom container was one of the following: 210,
(2 + s)" ((-- I~)"R1+")
P = Pa "4- m2.(n + 1) h 1+2" 270, 360 and 610 ram0 depending on the experiment.
In contrast with a conventional squeeze flow experi-
ment in which the diameters of platens are much
larger than the sample, a bottom container was used
to contain the fresh cement paste and the top plate
where P, is the atmospheric pressure. The total instant- penetrated the contained paste.
aneous force that must be applied to the disc at z = h Cement paste was poured into the bottom con-
is obtained from Equation 7 by integrating P over the tainer and adjusted to a given initial sample height by
surface of the disc. This results in the expression adjusting the weight of the cement paste; here, initial
sample heights were 18, 36, 54 and 72 mm. The bot-
(2 + s)" ( ( - /~)"R3+")
tom container and cement paste were placed on the
Fr~ = mn 2"(3 + n) hqTy~, j (8)
bottom plate of the servohydraulic machine. Then
the top plate was lowered. The interface between the
The average normal stress of a non-Newtonian fluid at top plate and the sample surface was controlled by set-
the plate can then be calculated: ting the initial load within the range - 0 . 1 to - 0 . 5 N
(compression). The squeeze displacements were 1,
FN (2 + s)" ( ( - h)"RI+") 5 and 10 mm and the squeezing period was 120 s.
O'Nav -- 1tR z - m2"(3 + n) h l+z" (9)
The load and displacement of the sample were
measured with a load cell and a linear variable differ-
If the definition of logarithmic strain rate is invoked,
ential transformer (LVDT). The load cell measured
then the above equation is expressed by
only the normal component of the load, and the aver-
(2 + s)" ( R ) ~+" (10) age normal stress was obtained by dividing the load
CYyav = m~" 2 (3 + n ) \ h by the area of the top plate. The capacity of the load
cell was 1000 N. Experiments were performed under
The parameters m and n are obtained by a trial and
error method using Equation 10, giving
m = 700 n = 0.2 (11) didata
splacquisitand
acement ioof
nload
From Equation 10, a geometric factor for power-law
fluids (PGF), which shows the effect of the dimension-
less geometric parameter, R/h, in squeeze flow can be
defined:
t
PGF = (12)

From Equation 10, and setting (~m : O'Nav, geometric

factor for fresh cement paste (CGF) is written as in'i~l
sidewall
ioppl~ate~I I T constantvelocity
a polynomial function of R/h:

CGF =
i=0
al (13) sampleinI~ii
itial i ii ~iiiii i i!i ii ilI ~la~gplte
where i includes the parameter n, a~ are constants bottomcontainer
obtained from curve-fitting to experimental results Figure 2 Schematic diagram of squeeze flow experimental system.
and k is taken as 3rd order in this experiment. The Initial sample height 18, 36, 54 or 72 ram; constant velocity 0.0083,
analytical result for normal stress using the geometric 0.0417 or 0.0833 m m s -1.

1376
T A B L E I Experimental conditions for constant-velocity flow ex-
periments 160

Initial sample Amplitude of Average logarithmic

height ramp signal strain rate 120
(mm) (mm) (s - i )
E
36 1 0.000 234 -~ 80
o r7
5 0.00126 --I

10 0.002 75
1 0.0048 40
18
5 0.002 75 8 8
10 0.0075
[]
1.0 1.4 1.8 2.2 2.6 3.0 3.4
D i a m e t e r ratio b e t w e e n b o t t o m and t o p

constant squeeze rate; that is, a constant lowering Figure 3 Effect of dimension of the bottom container on the peak
load: sample height (O) 18 mm, ([Z) 36 ram.
velocity of the top plate. The apparent normal strain is
expressed by using the definition of logarithmic strain

~(t) = In h~o } = In ho (15) tainer during the test. Larger diameters of the bottom
container prevent this, although the sample extends in
where h is the sample height, do the squeeze displace- the radial direction to the wall. This means that there
ment and ho the initial sample height. The apparent is a lower limit for the ratio of the diameters of the top
normal strain rate is given by plate and bottom container for which meaningful ex-
d~ /~ periments can be performed. In this experiment it was
k(t) -- dt - h(t) (16) found that the effect of a repulsive force from the wall
can be neglected at a diameter ratio larger than 1.7, as
where/~ is the constant velocity of the top plate. For suggested by the constant loads shown in Fig. 3.
analysis of these results, the average normal strain rate Therefore a bottom container diameter of 36 cm was
is obtained as the arithmetic mean of initial and final adopted for use in the main experiment.
normal strain rates. Table I shows the experimental
conditions for the constant-velocity squeeze flow ex-
periments. 4.2. Effect of buoyancy force on experiment
results
During the squeezing motion of the top plate an
4. A r t e f a c t s related t o a squeeze upward force is generated by the buoyancy of the top
experiment plate as it enters the paste. The buoyancy force B can
In a conventional squeeze experiment, the sample is be expressed as
loaded between top and bottom plates that have the
B = oVg (17)
same area. In this geometry the sample deforms in the
radial direction by squeezing vertically. Normally the where P is the density of cement paste and V is the
samples cannot flow under their own weight; however, volume of the top plate submerged in cement paste. In
cement paste can flow and therefore it must be con- our experiment, this effect was computed to be ap-
tained, introducing the unknown influence of the re- proximately 15% of the measured load. In other
stricting wall of the bottom container. Thus the effect words, the measured load is about 15% larger than
of varying the ratio of the diameter of the top plate to that at the top interface between plate and paste.
that of the bottom container must be established. This
was done by using a top plate of constant diameter
and four bottom containers with different diameters. 4.3. State of friction between top plate and
Another consideration was the buoyancy force of the surface of sample
top plate as it penetrates the paste. Finally, friction The effect of friction at the interface between top plate
between the top plate and the surface of the sample is and surface of sample was investigated by using motor
important because it causes a shear stress at the inter- oil (SAE-30), Teflon and sandpaper on both top plate
face during deformation. These potential problems and bottom container. Before doing these experi-
had to be investigated before squeeze flow experi- ments, cement paste was placed on a plate that was
ments could be interpreted. coated with either a lubricant or sandpaper and tilted
with respect to the horizontal. The Teflon coating
allowed the paste to slide better than did the motor oil,
4.1. Effect of the d i m e n s i o n s of the container so, Teflon was used to approach a frictionless condi-
The effect of the diameter of the bottom container on tion. Sandpaper produced sticking condition at the
the peak load, under otherwise identical experimental interface.
conditions, is shown in Fig. 3. If the bottom container Fig. 4 shows a plot of normal stress versus apparent
has nearly the same diameter as the top plate, then the strain (as defined by displacement) at constant velocity
cement paste overflows the wall of the bottom con- of the top plate for the two interfacial conditions. The

1377
 1000 10000 ........ , . . . . . . . . , . . . . . . . . , . . . . . .

0_ 0_
~1ooo
~0
+"
"~ 100 ~zx~
E
0
E
100:
z Z

10 J i 01.1 1 0 . . . . . ' . . . . . . . . i . . . . . . . . i . . . . ,,

0.0001 0.001 0.01 0.0001 0.001 0.01 0.1

Apparent strain Apparent strain
Figure 4 Effect of friction state on normal stress versus apparent Figure 5 Average normal stress versus strain for various average
strain: (O ) lubricant (Teflonspray),( [] ) sandpaper, ( A) non-lubric- apparent strain rates: (O) 0.000234 s- 1, ([]) 0.00048 s-1, (A) 0.001
ant. 26 s- 1, ( x ) 0.00275 s- 1, ( + ) 0.0075s- 1.

initial sample height was 36 mm and the squeeze dis- ments I-1]. The location of the beginning of region III
placement was 5 mm. In the case of sandpaper the depends on apparent strain rate, occurring at lower
results show that the highest load occurs initially, due values of apparent strain when the apparent strain
to friction between plate and surface of sample. By rates are smaller. Regions II and III show that the
comparing these results with those from the zero- behaviour of cement paste differs under different ex-
friction experiments, it is apparent that as the squeez- perimental conditions, and indeed the results from
ing of the sample progresses, the influence of the state shear flow and squeeze flow are opposite at large
of friction at the interface becomes less pronounced. In apparent strains, i.e. strain softening (shear flow) or
other words there is not much difference between strain hardening (squeeze flow).
lubricated and non-lubricated conditions except at the
initial stage of compression. There is no way of
measuring directly the shear stress due to friction; 5.2. M e c h a n i s m for strain hardening
therefore, it is difficult to analyse an experiment in Possible mechanisms for the strain-hardening behavi-
which friction plays a large role. The following results our under squeeze flow were investigated by the fol-
are obtained from experiments that used Teflon at the lowing experiments: (i) superplasticizer was added to
interface. paste, and (ii) tests were carried out using a combina-
tion of compression, rest (and associated relaxation)
and tension. A superplasticizer reduces the viscosity
5. Results and discussion and therefore should alter region III if it is a material
5.1. C e m e n t p a s t e property. Tensile stress is applied by increasing the
The average normal stress is related to the apparent distance between the plates and, once again, this will
strain for various average apparent strain rates (pro- provide insight into any geometric effects of strain
duced by varying initial sample heights or squeeze hardening, i.e. whether strain hardening is due to the
displacements) as shown in Fig. 5. The curves are plates approaching each other.
approximately S-shaped, and can be divided into three The effect of a superplasticizer on the relationship of
regimes regardless of the apparent strain rate. There is stress to apparent strain is shown in Fig. 6. Superplas-
much scatter of stress for small apparent strain rate, ticizer (ASTM C-494 type A) was added at 1% by
due in part to the reduced accuracy of the load cell at weight of cement. The data are plotted on linear scales
small loads. since strain hardening occurs at large deformation,
Region I shows a linear relationship between stress and also because there is much scatter of measured
and apparent strain. The range of region I increases stress at small strain due to the limits of accuracy of
with increasing apparent strain rate. Thus, cement the load cell. The results show that cement paste
paste exhibits a linear elastic region under squeeze exhibits strain-hardening behaviour both with and
flow conditions as well as under shear flow [1]. without superplasticizer, but the gradient of the in-
Region II is nearly flat, i]e. the stress increases only creasing stress is reduced by the addition of a super-
by a small amount with increasing apparent strain, or plasticizer. This means that strain hardening is caused,
in other words cement paste deforms plastically. This at least in part, by the geometry of the specimen.
is in contrast to the results from shear flow experi- Indeed, because paste is being squeezed out of the
ments, where the cement paste exhibited a structure region between the plates, the concept of strain breaks
breakdown after a yield point of greater stress than down completely at large displacements.
that needed to sustain region II [1]. The second group of experiments, cycled speci-
In region III, at large apparent strains, the normal mens through compression, rest and tension, each for
stress increases with increased apparent strain. This a period of 120 s. Fig. 7 shows a plot of normal stress
increasing stress is in contrast with a continuous struc- as a function of time for three 120 s periods. The
tural breakdown observed in shear flow experi- normal stress increases during compression of the top
1378
 I I I I I r i i~ pared with that of the compression curve. This may
800 mean that the packing of cement particles changes
during compression and tension. The peak stress at
600 the end of the unloading, or tension step is small
compared with that of compression step.

400
[ 5.3. E q u i v a l e n t s h e a r s t r e s s
200
A comparison of these results with results from shear
_ [3DDDDDDDD DDODOIDDD E~i~ flow techniques may be attempted by converting nor-
~;~.-~ c~3_o c-~o o o o c~ao o o 0,OoOQoOOCp~D
E~3LIDDDD mal stress and apparent strain to an equivalent shear
00"-'v0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 stress and strain, using the assumption of uniaxial
Apparent strain compression. Once again there are many assumptions
involved in this analysis. Perhaps the most notable is
Figure 6 Effect of superplasticizer on stress versus apparent strain:
(A) none, (D) 0.3% of cement weight (15g), (O) 1% of cement that difficulties associated with paste flowing out from
weight (50 g). between the plates and into the container, i.e. difficult-
ies associated with the definition of strain, are being
ignored. Also end-effects are being greatly simplified
2000 i in our analysis. However, some insight may be gained
from the analysis, particularly for small displacement.
1600 ~ .
The equivalent or resolved shear stress, Xeq, is ob-
1200 tained using Mohr's circle.

~' 800 1
17eq ---- ~O'zz (18)
400
Similarily, if the Poisson's ratio of fresh cement paste
Z is assumed to be 0.5 from the volume constancy (in
-400 other words, if an equibiaxial extensional flow is as-
sumed), the relationship between apparent shear
-800 . . . . . . strain and apparent normal strain components is also
0 80 100 150 200 250 300 350
"time (s) obtained using Mohr's circle.

Figure 7 Stress versus time under compression, rest and tension 3

~=, = ~ = (19)
cycle of top plate. Ratio of squeezing amplitude (mm) to initial
sample height (ram): (O) 5 36, ([]) 5 18, (A) 1018.
From the relationship T=, = 2e=,, the converted shear
strain, y=,, is given as
2000 i i

3
1600 A ~" 7=, = ~ z ~ (20)

~1200 A AAAAAAA
and the converted shear strain rate, ~=,, is
s 800 AA AA
3
~fz, = ~g= (21)
% 400
E
o
z
0

-400 RtAAAAAAAAAA A A A & A

-800 0 I I I I I |
A
A A

I
J I
Based on this analysis, Fig. 9 shows plots of shear
stress versus shear strain rate, obtained from shear
flow experiments in our earlier work rl], and equival-
ent shear stress versus equivalent shear strain rate
0.2 0.4 0.6 0.8 obtained from squeeze flow experiments. The shear
Apparent strain
and equivalent shear rates of large value produce
Figure 8 Stress versus apparent strain under compression, rest and stresses of high value. The experimental technique
tension cycle of top plate. Ratio of squeezing amplitude (mm) to apparently determines whether or not cement paste
initial sample height (mm); (O) 5 36, (rq) 5 18, (&) 10 18.
shows strain softening or strain hardening behaviour.
In other words, cement paste may have a different
plate, and it drops offas soon as the rest period begins. deformation process caused by shear than by squeeze
After the drop, the normal stress is constant, i.e. it is flow.
a residual stresses. Fig. 8 shows the normal stress as A comparison of flat (squeeze flow) and yield (shear
a function of apparent strain under the same condition flow) stresses as a function of strain rate is shown in
as shown in Fig. 7. The curves show a similar type of Fig. 10. The values of data points were obtained as
hysteresis loop regardless of experimental conditions. follows. Shear flow experiments [-1] were performed
During unloading, or during tension, cement paste for shear strain rates of 0.1, 0.2, 0.4, 0.8, 1.6 and
shows as elastic behaviour before the beginning of its 6.4 s- a. Squeeze flow experiments; however, were per-
plastic behaviour, although it has a gentle slope corn- formed at very small equivalent shear strain rates of

1379
 A

~1oooo

lOOO
1000-

lOO D_

1o
0 E
0
O
z o
Q ....... d . . . . . . . i . . . . . . . i ........ i ........ i ........ i ......

1o O.Ol 1 lOO
I00
Shear and equivalentshearstrain
Lx
Figure 9 Comparison of plots of stress versus apparent strain for I I IIlill D I 1 I llillt / I I I IllJlt I I I I I it
(9 shear and (Z]) squeeze experiments. Squeeze experiments: 0.0001 0.001 0.01 0.1
equivalent shear rates 0.00035, 0.00072, 0.00412, 0.00189, Apparent strain
0.011 25 s 1. Shear experiments:shear rates 0.2, 0.4, 0.8, 1.6,6.4 s - 1
High values of rate represent high values of stress. Figure 11 Comparison of measured and calculated stresses using
a geometricfactor for cement paste. Initial sample height = 18 mm.
Average apparent strain rate (measured): (A) 0.00049s -1, ([])
lOOO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.0032 s-1, (9 0.0104 s- 1; ( ) calculated from Equation 14.

viour under squeezing motion. Fig. 11 shows a com-

E parison of measured and calculated stresses using
0
Equations 14 according to average apparent strain
% lOO
rates with an initial sample height of 18 ram. There is
a good agreement, suggesting that at large strain the
"hardening" is due to non-Newtonian fluid behaviour
of cement paste. However, the initial apparent strain
region apparently does not follow non-Newtonian
1o fluid behaviour. Thus, there is a limitation to the
0.0001 0.001 0.01 0.1 1 10
Shear and equivalent shearrate(s-1) non-Newtonian fluid model at very small apparent
strains. Perhaps at very small apparent strains cement
Figure 10 ([~) Yield shear and (9 fiat normal stresses as a function
of apparent strain rate. Power laws: flat stress 493.6 Yeq"
o.275, shear paste behaves like a solid. Although there is good
stress 76 9 o.55. agreement, the analysis must be interpreted with cau-
tion.
0.00035, 0.00072, 0.001 89, 0.004 12 and 0.011 25 s -~.
The equivalent yield shear stresses are taken as the
stresses that are at the boundary between regions 6. Conclusion
I and II in Fig. 5. The flat normal stresses are deter- Normalized results from squeeze flow experiments do
mined at normal apparent strain value intermediate not agree with those from shear flow experiments. The
between the beginning and ending of region II, which difference between shear and squeeze is, perhaps, due
may be interpreted as a yield stress from squeeze to the different geometry of deformation of sample. In
experiments. spite of the difficulties mentioned in the section on the
These two stresses are modelled by power-law equa- relation of artefacts to squeeze experiments, an experi-
tions as shown in Fig. 10 for shear strain rate and mental technique for measuring the squeeze flow char-
equivalent shear strain rate, respectively. If these ma- acteristics of cement paste has been developed. It
terials and tests were showing material behavi0ur, the provides important new information about the rhe-
yield shear stress and the equivalent flat shear stress ology of cement paste under conditions where stable
would lie on the same line and have the same power- shear planes are suppressed. The results may be rel-
law index and coefficient. However, the results show evant to processes such as extrusion.
different power-law indices and coefficients: the Theoretical and experimental analyses of the
power-law indices differ by approximately a factor of rheological characteristics of cement paste under
two, and the power-law coefficients differ by a factor squeeze flow conditions are discussed. This behaviour
of six. Either different properties are being measured is divided into elastic (at small apparent strain), plastic
by the different experiments, or one or the other of the (after yielding) and strain hardening (at large apparent
results is fallacious. strain) regions. The latter region is similar to that
often exhibited by solid-like deformation behaviour.
5.4. C o m p a r i s o n o f a n a l y t i c a l a n d On the other hand, strain hardening at large apparent
e x p e r i m e n t a l results strain is analysed by considering the paste to be a non-
The rheological behaviours in regions II and III in Newtonian fluid obeying a power law. This analysis
Fig. 5 are analysed using non-Newtonian fluid beha- shows good agreement between experiment and the-

1380
ory, indicating that the strain hardening is a con- 11. P . F . G . B A N F I L L and D. R. K I T C H I N G , in Proceedings of
sequence of the geometry of the measurement process. International Congress on Rheology of Fresh Cement and
Concrete, edited by P. F. G. Banfill (University Press. Cam-
These results indicate that cement paste, at large de-
bridge, 1991)p. 125.
formation, behaves like a non-Newtonian fluid. 12. G . J . DIENES and H. F. KLEMM, .I. Appl. Phys. 17 (1946)
458.
13. G . J . DIENES, J. Coll. Sci. 2 (1947) 131.
Acknowledgements 14. R. J. G R I M M , AIChE J. 24 (1978) 427.
The authors would like to express their appreci- 15. K . S . G A N D H I and R. BURNS, Trans. Soc. Rheol. 20 (1976)
ation to Concrete Technology Corporation of Santa 489.
Barbara, California, for instrumentation and financial 16. R . J . SILVA-NIETTO, B. C. FISHER and A. W. BIRI.Y,
support of this work, and the National Science Foun- Polym. Enyn 9 Sci. 21 (1981) 499.
17. E . J . D I C K E N S O N and H. P. WITT, Trans. Soc. Rheol. 13
dation Center for Advanced Cement Based Materials,
(1969) 485.
grant DMR-88080432. It is with regret that we report 18. A . N . GENT, Br. J. Appl. Phys. 11 (1960) 85.
that Professor Lewis Erwin died during the final 19. M . J . FOSTER, J. Appl. Phys. 26 (1955) 1104.
stages of this research. 20. S . H . CHATRAEI. C. W. M A C O S K O and H. II. WINTER,
J. Rheo/. 25 (1981) 433.
21. A. T E R E N T Y E V and G. K U N N O S , in Proceedings of Inter-
national Congress on Rheology of Fresh Cement and Con-
References crete, edited by P.F.G. Banfill (Cambridge University Press,
1. B.H. MIN, L.ERWIN, and H. M . J E N N I N G S , Ceram. "['rans. Cambridge, 1990) p. 93.
16 (1990) 337. 22. M. REINER, in "Rheology", Vol. 3, edited by F. R. Eirich
2. Idem, Korean J. of Rheol., in press. (Academic, New York, 19(-,0) p. 351.
3. G. H. TATTERSALI., Nature 175 (1955) 166. 23. R.B. BIRD, R. C. A R M S T R O N G and O. HASSAGER, "Dy-
4. R. LAPSIN, Cemento 4 (1982) 243. namics of Polymeric Liquids", Vol. 1, (Wiley, New York 1977)
5. W. VOM BERG, in Proceedings of 8th Internationl Congress p. 429.
on Rheology, Vol. 3 (Plenum, New York, 1980) p. 665. 24. W. OSTWAI.D, V. K O L L O I D - Z . 36 (1925) 99.
6. I. ODLER, T. B E C K E R a n d B . WEISS, Cemento (1978) 303. 25. A. I)e WAELE, Oil & Color Chem. Assoc. J. a (1923) 23.
7. P . F . G . BANFILL, Mag. Contr. Res. 33 (1981) 37. 26. P . J . LEIDER and R. I~. BIRD, in "Industrial Engineering
8. T . E . R . JONES, G. BRINDLY and B. C. PATEI., in "Hy- Chemical Fundamentals", Vol. 13 (American Chemical So-
draulic Cement Pastes: Their Structure and Properties", Pro- ciety, Washington, 1974) p. 336.
ceedings of Conference, University of Sheffield, 1976, p. 135.
9. A.R. CUSEN and J. HARRIS, in Proceedings of RILEM, on
"Fresh concrete; important properties and their measure-
ments, Sem'. Leeds, England, 1973. Vol. 1 (Dept. of Civil Received 28 July
Engng. University of Leeds, Leeds, England, 1973) p. 2.8.1. and accepted 26 August 1993
10. T. M. C H O W , L. V. M c l N T I R E , K. R. K U N Z E and C. E.
COOK E, SPE Prodn Enyn 9 3(4) (1988) 543.

1381