ACI MATERIALS JOURNAL
Title no. 105-M33
Correlation between Paste and Concrete Flow Behavior
by Julissa Hidalgo, Chun-Tao Chen, and Leslie J. Struble
The correlation between cement paste rheology and concrete
workability in mixtures containing a polycarboxylated acrylate
ester was initially seen as poor, in that the admixture dosage
required to produce full dispersion in cement paste, as determined
using dynamic rheology, was approximately four times the dosage
required to produce full dispersion in concrete, as determined
using slump and slump loss. A preshear protocol using a high-
speed blender to reduce differences in shear history between
cement paste and concrete provided a much improved correlation
between paste rheology and concrete workability. Adsorption
isotherms verified that both pastes and concretes were at full
admixture saturation when fully dispersed.
Keywords: cement paste; high-range water-reducing admixture; rheology;
shear; slump; yield.
INTRODUCTION
Concrete workability is defined as “the amount of
mechanical work, or energy, required to produce full
compaction of the concrete without segregation”1 and is
generally related to the concrete fluidity. Because cement
paste is the liquid phase in concrete, its flow properties are
reasonably expected to correlate with concrete workability.
Rheological properties of cement paste, a viscoelastic
material, include yield stress, viscosity as a function of strain
rate, and dynamic shear modulus as a function of strain. For
many years, the authors’ research group has been using
dynamic rheology to study cement paste, in particular, the
progressive stiffening due to cement hydration reactions2
and the interactions between portland cement and
dispersing admixtures.3 Because paste plays a major role
in concrete workability, it was assumed throughout this
work that there is a direct relationship between paste and
concrete flow behavior. The goal of this study was to
explore that relationship in mixtures containing high-
range water-reducing admixtures.
The correlation between paste and concrete flow behavior
is especially important because measuring rheological
properties of concrete is very difficult. Slump, the standard
field measurement of concrete workability, has been shown
to correlate with yield stress4 but provides no information
about viscosity. Designing a rheometer to measure concrete
viscosity is very complicated because the large gap required
for concrete makes slip very likely, and the use of vanes to
reduce slip lead to uncertainties in the rheological properties.
A recent study showed a very poor correlation between
several concrete rheometers currently available, probably
reflecting these complications.5
Rheological properties of cement paste, on the other hand,
can be measured with considerable accuracy and precision.
In particular, dynamic rheometry was found to provide a
highly accurate and sensitive measure of flow behavior and
allows one to measure yield stress without the slip often
associated with large strains.2 Using paste to study flow
ACI Materials Journal/May-June 2008
TECHNICAL PAPER
behavior offers many potential benefits over concrete, not the
least of which is the ability to use dynamic rheometry.
In a previous paper, Struble and Chen 4 reported only a
weak correlation in flow behavior between concrete and
paste, and the research reported herein was designed to
explore the relationship more carefully in mixtures
containing a high-range water-reducing admixture. Dynamic
(oscillatory shear) measurements on paste were used to
determine the viscoelastic properties and the admixture
dosage response (dosage needed for full dispersion).
Concrete slump and slump loss were used to determine the
concrete workability and the admixture dosage response.
The dosage response between paste and concrete was
compared. In preliminary experiments, Struble and Chen4
found that the cement paste and concrete did not correlate
well—the admixture dosages for full dispersion were much
lower in concrete than in paste. It was then proposed that
agreement in admixture dosage could only be obtained when
the cement paste was given the same shear history as it
experiences in concrete. Therefore, in the main experiments,
the paste was presheared using a high stress protocol shown
by Helmuth et al.6 to reproduce the contribution of aggregates in
shearing cement paste in concrete. Because slump is an
uncertain measure of concrete yield stress, adsorption
isotherms were also used to determine whether the
admixture dosage that produced high slump and slump
loss corresponded to the dosage that produced full dispersion.
This work is presented in greater detail in two theses.7,8
RESEARCH SIGNIFICANCE
The development of new technologies for achieving
highly workable concrete demands knowledge of paste and
concrete rheology, so research in these areas is very important in
concrete science and technology. Use of a high-shear preshear
protocol for paste produced a direct correlation between the
dosage of dispersing admixture in paste and concrete. This
correlation suggests that paste rheology can be used to set the
target dosage of water-reducing admixtures in concrete and
to determine the nature of cement-admixture interactions,
thereby using less material and taking advantage of the
greater accuracy and precision of paste rheology.
EXPERIMENTAL PROCEDURE
Materials
Several commercial portland cements were used during
this study. In the preliminary experiments, Cements C1, C2,
and C3 were used, which were obtained from a single
manufacturer and used in previous studies.2-4 In the main
ACI Materials Journal, V. 105, No. 3, May-June 2008.
MS No. M-2007-097.R1 received March 15, 2007, and reviewed under Institute
publication policies. Copyright © 2008, American Concrete Institute. All rights reserved,
including the making of copies unless permission is obtained from the copyright proprietors.
Pertinent discussion including authors’ closure, if any, will be published in the March-
April 2009 ACI Materials Journal if the discussion is received by December 1, 2008.
281
 content of 28.58% measured according to ASTM C1017,
Julissa Hidalgo is an Assistant Materials Technologist at CTLGroup, Skokie, IL. She
received her BS in civil and environmental engineering from the University of Puerto “Standard Specification for Chemical Admixtures for Use in
Rico-Mayaguez Campus, Mayaguez, Puerto Rico, and her MS in civil and environmental Producing Flowing Concrete.”
engineering from the University of Illinois at Urbana-Champaign, Urbana, IL. Her
research interests include rheology of cement and concrete. The aggregates used to make concrete were a crushed
limestone and a natural siliceous sand. Their physical
ACI member Chun-Tao Chen is an Assistant Professor at the National Taiwan University properties are summarized in Table 2.
of Science and Technology, Taipei, Taiwan. He received his BS in engineering from
National Taiwan University; his MS in harbor and river engineering from National
Taiwan Ocean University, Keelung, Taiwan; and his PhD in civil and environmental
engineering from the University of Illinois at Urbana-Champaign. His research
Paste rheology
interests include rheology of cement and concrete and the interactions between During this study, the oscillatory shear technique was used
cement and dispersing admixtures. to measure the rheological properties of pastes containing
Leslie J. Struble, FACI, is a Professor in civil and environmental engineering at the variable amounts of CAE. An oscillatory shear stress was
University of Illinois at Urbana-Champaign. She received her BS in chemistry from applied to the material and the resulting strain was measured,
Pitzer College, Claremont, CA, and her MS and PhD in civil engineering from Purdue from which one can compute the storage modulus. By
University, West Lafayette, IN. She is a member of ACI Committee 236, Material
Science of Concrete. Her research interests involve the chemistry, microstructure, and varying the amplitude of the stress and examining the
engineering properties of cement and concrete, including rheology of cement paste storage modulus as a function of stress, one can determine
and concrete.
the yield stress; on increasing the stress, the yield stress is the
stress when the storage modulus decreases, typically by
experiments, Cement B (Type I/II) was used. The compositions several orders of magnitude.
of all these cements are given in Table 1. The surface area of The paste experiments were conducted at a fixed water-
Cement B, determined using nitrogen gas adsorption, was cement ratio (w/c) (by mass) of 0.35. Dosages of CAE varied
1.490 m2/g (454.7 ft2/oz). from 0.01 to 0.70% (herein the admixture dosage is given as
The dispersing admixture was a commercial carboxylic solid CAE relative to the mass of cement). In all experiments,
acrylate ester (CAE), which met the requirements of ASTM zero time was taken when cement and water first came
C494, “Standard Specification for Chemical Admixtures into contact.
for Concrete,” for Type F high-range water-reducing In the preliminary experiments, approximately 2 mL
admixture. In the preliminary experiments, the same CAE (0.07 fluid oz) of paste were mixed by hand for approxi-
was used that was used in a previous study.3 In the main mately 2 minutes. The paste was then transferred to the
experiments, a different CAE was used: a liquid with a solids rheometer, an additional preshear applied, and rheological
measurements were begun.
In the main experiments, a larger volume of paste was
Table 1—Chemical composition of cements* mixed using a high-shear, water-cooled, speed-controlled
Chemical
Percent by weight blender. The blender had a minimum speed of 4,000 rpm and
constituent Cement C1 Cement C2 Cement C3 Cement B a maximum speed of 12,000 rpm. The protocol was based on
SiO2 20.4 22.5 20.0 20.6 that developed by Helmuth et al.6 to produce paste with
Al2O3
similar set behavior as concrete by applying a mixing shear
5.3 3.3 5.2 5.0
rate of approximately 2200 s–1 for several minutes. The
Fe2O3 2.3 3.9 2.4 2.4 blender protocol was as follows: the cement, 500 grams
CaO 61.9 63.7 63.1 64.1 (17.6 oz), was first sheared for 1 minute to break any
MgO 1.5 2.7 2.7 2.9 agglomerates; the blender was then stopped and the
SO3 4.2 2.1 2.9 2.4 appropriate amount of water and admixture solution were
Calculated composition added within a period of 30 seconds; the paste was sheared
C3S 46 57 58 61
for 30 seconds at low speed; the blender was stopped for
1.5 minutes, during which the walls were scraped with a
C3A 24 2 10 9 spatula to provide uniform mixing; and the paste was
Total alkali sheared for another 1.5 minute at high speed. Approximately
(Na2O equivalent) 0.97 0.42 0.35 0.18
2 mL (0.07 fluid oz) of the paste was then transferred to
*
Provided by manufacturers. the rheometer, a preshear applied, and rheological
measurements were begun.
Table 2—Aggregate properties The rheometer used for this study was operated using
stress-controlled oscillatory shear. The experiments used a
Coarse aggregates Couette geometry with a 14.0 mm (0.551 in.) diameter
Nominal maximum size 25.4 mm (1.0 in.) smooth bob and a 15.4 mm (0.606 in.) diameter smooth cup,
Unit weight (OD) 1630 kg/m3 (102 lb/ft3) for a 0.7 mm (0.028 in.) gap between the bob and cup. The
Degree of absorption 1.46% temperature was controlled at 25 °C (77 °F) by water that
Free water 0.4% circulated around the cup. The rheometer and data acquisition
Specific gravity (SSD) 2.67
were controlled by a computer. Regardless of the type of
mixing, paste was presheared in the rheometer at 200 Pa
Specific gravity (OD) 2.63
(0.029 psi) for 45 seconds and then allowed to equilibrate for
Fine aggregates
300 seconds to provide a uniform starting condition, a
Fineness modulus 2.63 procedure that is used routinely in these types of measurements.
Degree of absorption 1.52% Oscillating stress was then applied using a frequency of 1 Hz
Free water 0.54% (1 s–1) and an amplitude that was increased from 0 to
Specific gravity (SSD) 2.62 1000 Pa (0 to 0.1450 psi).

282 ACI Materials Journal/May-June 2008

Concrete workability
The concrete mixture was designed using the absolute
volume method described in the ACI 211.1-91, “Standard
Practice for Selecting Proportions for Normal, Heavyweight,
and Mass Concrete.” The w/c was 0.35—the same as for the
paste. The target slump was 25 mm (1.0 in.). The mixture
design is summarized in Table 3. The concrete experiments
used Cement B, the same as in the paste.
For the preliminary experiments, concrete was prepared
using a drum mixer and a slightly different procedure from
the main experiments (as follows). Cement and fine
aggregate were mixed for 1 minute, water and admixture
solution were added, and the mortar was mixed for
approximately 2 minutes, and then coarse aggregate was
added and the concrete mixed for approximately 3 minutes.
For the main experiments, concrete was prepared using a
0.1 m3 (3.5 ft3) pan mixer, with the mixing pan rotating
at 10 rpm. The mixing procedure for concrete was based on
ASTM C192-02, “Standard Practice for Making and Curing
Concrete Test Specimens in the Laboratory,” (mixing for
3 minutes, resting for 3 minutes, and mixing for 2 minutes)
except for minor variations in the mixing time and the
admixture addition. Both aggregates, fine and coarse, were
placed in the pan mixer and mixed for 1 minute to obtain
good uniformity. To mimic the mixing procedure used for
paste, the entire water and admixture solution was added at
the beginning and mixed for 1 additional minute. The pan
mixer was stopped, the cement was added, and the concrete
was mixed for 3 minutes, allowed to rest for 3 minutes
(during which time the pan was scraped), and then mixed
again for 2 minutes.
As soon as the concrete was mixed, concrete slump tests
were conducted according to ASTM C143-03, “Standard
Test Method for Slump of Hydraulic-Cement Concrete.”
Four cones were filled. One slump was measured as soon as
the cone was filled, and the others were measured at 10- to
15-minute intervals to determine slump loss.
X-ray diffraction
The mixing procedures for paste and concrete differed
slightly, in that the paste was mixed for 4 minutes and the
concrete for 8 minutes. The difference may be negligible
because all tests were carried out at the beginning of the
dormant period. Powder X-ray diffraction (XRD) was used
to determine whether the difference in mixing time caused
differences in the formation of hydration products between
paste and concrete. If there is no difference between these
hydration times, it is reasonable to conclude that this short
difference in time between paste and concrete did not affect
the rheology study.
The cement pastes (made using Cement B) were mixed by
hand for 1 minute at 25 °C (77 °F) using deionized water,
w/c of 0.35, and 0.13% of CAE. The hydration was
stopped at 4 minutes and 8 minutes to mimic the two mixing
times explained previously, using the following procedure.
A 20 mL (0.7 oz) glass bottle was filled approximately one-
third with paste and filled to the top with methanol (shaking
to mix and dilute the water). The cement was allowed to
settle, the methanol-water liquid was carefully removed by
pipette, and fresh methanol was added (shaking to mix).
After 1 hour, the liquid layer was again removed by pipette
and fresh methanol was added (shaking to mix). The sample
was stored in this way until it was analyzed. Just before analysis,
the methanol was removed by pipette, the specimen was
ACI Materials Journal/May-June 2008
ground in a mortar and pestle to a particle size of approximately
10 μm (0.0004 in.), methanol was allowed to evaporate, and the
ground sample was packed into the sample holder from the
back with modest hand pressure.
The X-ray diffractometer collected data from 5 to 70 degrees
(2 θ) with a step size of 0.02 degrees and a dwell time of
1.5 seconds. The working voltage was 40 kV and the current
was 40 mA.
Adsorption measurements
As part of the main experiments, adsorption isotherms for
CAE in paste and concrete were conducted to determine
whether the dosage producing high slump and slump loss in
concrete corresponds to the dosage required for full
dispersion. These measurements were made by filtering the
sample and then measuring the total organic carbon (TOC)
in the liquid to determine the amount of adsorbed admixture.
It was first necessary to perform a calibration to determine
the relationship between TOC and CAE concentration. First,
3.710 g (0.112 oz) of the thick CAE solution were transferred to
a 100 mL (3.520 oz) volumetric flask and brought up to
volume with deionized water, giving 0.0106 g of CAE per
mL solution (0.0106 oz CAE per fluid oz solution). Dilutions
of this solution were prepared volumetrically to provide
eight solutions of various concentrations for calibration. A
linear relationship between the concentrations of carbon and
CAE was observed (Fig. 1).
For cement paste, collecting the solution for TOC was
begun within 5 minutes after mixing. Paste was centrifuged
for 5 minutes at 6000 rpm and the resulting solution was
transferred into a syringe and filtered through a 0.45 μm
(0.00002 in.) paper filter. This solution was then centrifuged
for a second time at 6400 rpm for 5 minutes to eliminate very
small particles and finally filtered again with a syringe and a
0.45 μm (0.00002 in.) filter. For concrete, the coarse aggregate
was first removed by sieving the concrete through a 4.75 mm
Fig. 1—Calibration curve for determination of CAE
concentration from results of total organic carbon
(TOC) (x-axis ranges from 0 to 0.032 oz C per lb solution and
y-axis ranges from 0 to 0.0037 oz C per fluid oz solution).
Table 3—Concrete mixture design (saturated
surface dry basis)
Cement, Water, Coarse aggregate, Fine aggregate,
kg/m3 (lb/ft3) kg/m3 (lb/ft3) kg/m3 (lb/ft3) kg/m3 (lb/ft3)
510 (31.8) 179 (11.2) 1120 (69.9) 590 (36.8)
283
(No. 4 mesh) sieve, and the resulting mortar was centrifuged
and the solution filtered as described for paste. Because
concrete was made using tap water, a sample of this water
was also analyzed by TOC. Several aliquots of each sample
were used to measure TOC and the adsorbed CAE was
computed using the calibration curve.
Fig. 2—Paste stress sweeps in preliminary experiments
using varying amounts of CAE and: (a) Cement C1; (b)
Cement C2; and (c) Cement C3 (from Reference 3, used with
permission) (x-axes range from 1.45 × 10–5 to 1.45 × 10–1 psi
and y-axes range from 1.45 × 10–7 to 1.45 × 103 psi). (Note:
1 psi = 0.000145 Pa.)
284
RESULTS
Paste rheology
Paste rheology results are shown as stress sweeps (plots of
dynamic storage modulus as a function of stress). In general,
the pastes with 0% CAE had a high storage modulus at low
stress and a high yield stress (stress at which the storage
modulus decreased, indicating flow) characteristic of a
flocculated microstructure. The pastes with high dosages of
CAE had a very low storage modulus at all stress levels and
no yield stress (at least not in the stress range that can be
measured), characteristic of a fully dispersed microstructure.
Pastes with intermediate dosages of CAE showed intermediate
values of modulus and yield stress, characteristic of
microstructures with intermediate flocculation. As CAE
dosage was increased, the pastes became progressively more
dispersed. As has been observed previously,3,9 the storage
modulus decreased by several orders of magnitude with
increasing dosage of CAE. As noted previously,3 the authors
consider this type of behavior, a progressive increasing
dispersion with increasing admixture dosage, to represent
classical dispersion.
The rheology results of the three cements in the preliminary
experiments, which were reported previously,3 are shown in
Fig. 2(a), (b), and (c). With no CAE, stress sweeps were all
characteristic of flocculated paste, and with high dosage of
CAE, the stress sweeps became characteristic of dispersed
paste. Two of the cements used in the preliminary experiments,
Cement C2 and C3 (Fig. 2(b) and (c)), showed a slight gelation
at intermediate dosages of CAE. For Cement C2, the gelation at
0.10 to 0.20% CAE was relatively strong. The gelation is
indicated by: 1) increased storage modulus, similar to the
modulus observed with no CAE; and 2) high yield stress,
higher than the yield stress observed with no CAE and higher
than the maximum value of 300 Pa (0.044 psi) used in these
stress sweeps. Higher dosages of 0.25 to 0.40% CAE showed
decreasing flocculation and increasing dispersion. For
Cement C3, the gelation was relatively weak at 0.10%
CAE, indicated by high storage modulus, similar to the
modulus of 106 Pa (145 psi) observed with no CAE, and
high yield stress, 100 Pa (0.015 psi), higher than the stress
of 20 Pa (0.003 psi) observed with no CAE. Higher dosages
of 0.15 to 0.40% showed decreasing flocculation and
increasing dispersion.
Cement B in the main experiment (Fig. 3) showed the
same behavior described for Cement C1. With no CAE,
the paste was flocculated, with a low-strain storage
modulus of approximately 105 Pa (14.5 psi) and a yield
stress of 10 Pa (0.001 psi). With an increasing dosage of
CAE, the pastes became decreasingly flocculated and
increasingly dispersed. There was no gelation at intermediate
CAE dosages. Full dispersion was observed at 0.13% CAE.
The CAE dosage required for full dispersion of Cement B
was considerably lower than the dosage required for full
dispersion of Cements C1, C2, and C3. This difference in
dosage is attributed to the high-shear preshear protocol used
with Cement B. It was previously reported3 that this preshear
protocol reduced both the storage modulus and the yield stress of
pastes, especially pastes containing high-range water-
reducing admixtures.
Concrete workability
Concrete slump results are shown in Fig. 4 for the preliminary
experiments and Fig. 5 for the main experiments. Slump
values increased dramatically with addition of CAE, from
ACI Materials Journal/May-June 2008
approximately 10 mm (0.3937 in.) for concretes with no
CAE (somewhat higher for C2) to 200 to 250 mm (7.87 to
9.84 in.) for concretes with ≥0.1% CAE. In mixtures with
dosages <0.1% CAE, the slump value was initially high but
decreased substantially during the 1-hour test duration.
High slump and slump retention were obtained only at
the highest CAE dosages (approximately 0.13% for
Cement C1, 0.11% for Cement C2, 0.11% for Cement C3,
and 0.13% for Cement B). Above these dosages, segregation
was observed, indicated by the separation of aggregate and
paste and sometimes by bleeding, so higher dosages were
not tested.

Hydration
Because paste and concrete were mixed for different
periods of time (4 minutes for paste and 8 minutes for
concrete), it was important to look for any difference in the
degree of hydration. Especially important was the formation
of ettringite (AFt), which may affect the rheological properties
of cement paste and concrete, and the formation of calcium
hydroxide (CH), which may accompany formation of poorly
crystalline calcium silicate hydrate, which may also affect
rheological properties of paste and concrete.
To determine whether the difference in time affected the
rheological properties, two samples of hydrated cements
(one hydrated for 4 minutes and 8 minutes) were analyzed
using XRD. As shown in Fig. 6, the XRD patterns appear to
be the same and neither AFt nor CH was observed in either
sample. Therefore, the difference in mixing time between
paste and concrete can be ignored.

Adsorption
Figure 7 shows the amount of CAE adsorbed by Cement B
in paste and concrete plotted as a function of CAE dosage
(commonly called an isotherm). The dashed line indicates
the admixture dosage required for full dispersion according
to the stress sweeps, 0.13%. Kirby and Lewis9 reported a
similar isotherm for CAE in paste. They reported that the
amount of CAE adsorbed relative to the cement surface area
at the critical weight fraction was 1.35 mg/m2 (59 oz/in.2). Fig. 4—Concrete slumps in preliminary experiments using
The adsorption at the critical weight fraction in Fig. 7 was varying amounts of CAE and: (a) Cement C1; (b) Cement C2;
and (c) Cement C3 (y-axes range from 0 to 11-3/4 in. [0 to
300 mm]).

Fig. 3—Paste stress sweeps in main experiment using varying

amounts of CAE and Cement B (x-axes range from 1.45 × Fig. 5—Concrete slumps in main experiment using varying
10–5 to 1.45 × 10–1 psi and y-axes range from 1.45 × 10–7 to amounts of CAE and Cement B (y-axis ranges from 0 to
1.45 × 103 psi). (Note: 1 psi = 0.000145 Pa.) 11-3/4 in. [0 to 300 mm]).

ACI Materials Journal/May-June 2008 285

somewhat higher, 3.75 mg/m2 (165 oz/in.2), not surprising
because different admixtures were used.
It is expected that the saturation of paste with admixture
would produce a dispersed microstructure and that additional
Fig. 6—XRD patterns (Cu-Kα) for Cement B paste hydrated
for 4 minute and 8 minutes showing absence of peaks attributed
to AFt and CH (at positions indicated by dotted vertical lines)
(8-minute pattern has been offset in intensity).
Fig. 7—Adsorption isotherms of CAE admixture in paste
and concrete, Cement B (y-axis ranges from –88 to 439 oz/in.2).
(Note: 1 oz/in.2 = 0.023 mg/m 2.)
Fig. 8—Types I and II adsorption isotherms (often called
BET classification), where W/Wm is weight adsorbed (relative
to weight at monolayer coverage) and P/Po is vapor pressure
(relative to saturation pressure) (calculated using BET
equations from Reference 10 with C = 100).
286
admixture above saturation would remain in solution. Such
behavior produces a Type I adsorption isotherm as described
by Brunauer et al. (reported by Lowell and Shields10)
(Fig. 8(a)), characterized as chemisorption and encountered
when adsorption is limited to few molecular layers, causing
the adsorption to level off when P/P0 is increased such that
all adsorption sites are filled. Kirby and Lewis9 reported that
sulfonated naphthalene formaldehyde adsorption showed
such Type I behavior. The CAE, on the other hand, appears
to follow a Type II adsorption isotherm (Fig. 8(b)), encoun-
tered when multiple layers are adsorbed and the adsorption
at saturation is infinite. Although it is not easy to identify
precisely the dosage at full saturation in a Type II isotherm,
it can be seen in Fig. 7 that the isotherm has an inflection
point or knee of approximately 0.13% CAE for both paste
and concrete, which can reasonably be taken as an esti-
mate of the completion of the first adsorbed monolayer.
DISCUSSION ON COMPARISON OF PASTE
AND CONCRETE BEHAVIOR
In the preliminary experiments, there was no agreement in
the behavior of paste and concrete or in the admixture dosage
for full dispersion in paste and concrete (Table 4). Although
the CAE dosages used in concretes were within the
recommended range, the dosage for full dispersion in
concrete was approximately one-fourth that in paste. A similar
difference in dosage between paste and concrete for sulfonated
naphthalene formaldehyde admixture was observed.8
Quite different behavior was observed in the main
experiments. When pastes were first presheared using the
high-shear protocol, results from paste rheology and
concrete workability were very similar. Both paste and
concrete were classically dispersed by CAE. Paste rheological
properties, yield stress and elastic modulus, decreased as
the dosage of CAE increased (Fig. 3) and concrete slump
increased as the dosage of CAE increased (Fig. 5). The
dosage for full dispersion in paste was 0.13% CAE, as
indicated by zero yield stress, and the dosage for full
dispersion in concrete was 0.13% CAE, as indicated by
maximum slump and no slump loss.
The objective of the adsorption measurements was to test
our interpretation that the admixture dosage in concrete
producing maximum slump and no slump loss indicates full
dispersion, in part because the authors could not check
slumps at higher CAE dosages due to concrete segregation. The
segregation made slump measurements unreliable but was
not expected to affect the adsorption behavior. The adsorption
results showed that the interpretation was valid. The admixture
dosage that provided maximum slump and slump retention
(Fig. 5) also produced full saturation (Fig. 7). Lower dosages
produced slump loss, much lower dosages produced lower
maximum slumps, and higher dosages produced segregation.
It should be noted that the coincidence of adsorption
behavior between concrete and paste would probably not
Table 4—Dosages for full dispersion in preliminary
experiments (percent solid CAE by weight
of cement)
Cement Paste, % Concrete, %
C1 0.7 0.13
C2 0.4 0.11
C3 0.4 0.11
ACI Materials Journal/May-June 2008
have been observed if the mixing procedures had not been so
closely duplicated.
Figure 9 summarizes the paste rheological parameters
(storage modulus and yield stress) and concrete workability
(initial slump) as a function of admixture dosage. From such
plots it is possible to estimate the admixture dosage that
produced full dispersion. Because yield stress shows a linear
relationship with dosage, it allows the most precise estimation of
admixture dosage for full dispersion.
Fig. 9—Paste and concrete values as function of admixture
dosage, Cement B: (a) paste storage modulus; (b) paste
yield stress; and (c) concrete initial slump (y-axes range
from: (a) 1.45 × 10–6 to 1.45 × 102 psi; (b) 0 to 1.45 × 10–3 psi;
and (c) 0 to 11-3/4 in.). (Note: 1 psi = 0.000145 Pa; 1 in. =
25.4 mm.)
ACI Materials Journal/May-June 2008
These data provide an opportunity to evaluate the relationship
between concrete slump and the yield stress of paste.
According to Tattersall and Banfill,11 concrete slump shows
a negative linear correlation with yield stress. In earlier
work, Struble and Chen4 reported an inverse but curvilinear
(exponential) relationship between concrete slump and yield
stress. Figure 10(a) shows a relationship between concrete
slump (initial slump value) and paste yield stress similar to
that reported by Struble and Chen,4 and fitting with an
exponential trendline gave a good correlation (R2 =
0.98). Figure 10(b) shows a similar relationship between
concrete slump and paste storage modulus (average of each
measurement in the linear viscoelastic region), with a
downward trend and a good linear correlation (R2 = 0.97)
when plotted in this way. Modulus values were plotted
using a logarithmic axis because the authors previously4
found such a relationship for several types of dispersing
admixtures, though CAE mixtures had poor reproducibility. In
the present study, the CAE mixtures showed a very strong linear
relationship, perhaps because the authors were more careful to
use the same mixing protocol for paste and concrete.
The focus of this research was to explore the correlation
between the rheological properties of paste and the slump of
concrete and to consider whether the effects of dispersing
admixtures are the same in paste and in concrete. Using a
single concrete mixture, a clear relationship between paste
Fig. 10—Initial concrete slump as function of paste (Cement B):
(a) yield stress; and (b) storage modulus (x-axes range from:
(a) 0 to 1.45 × 10–3 psi; and (b) 1.45 × 10–6 to 1.45 × 102 psi
and y-axes range from 0 to 11-3/4 in. [0 to 298.45 mm]). (Note:
1 psi = 0.000145 Pa.)
287
rheological properties (yield stress and dynamic storage
modulus) and concrete slump was observed. There are
numerous additional parameters that influence the slump of
concrete (for example, concrete constituents, mixture
proportions, and mixing procedure). These parameters need
to be considered in any attempt to predict concrete slump
based on measured rheological properties of paste.
SUMMARY AND CONCLUSIONS
The experimental findings and conclusions in this study
are summarized as follows:
1. The yield stress and storage modulus of paste both
decreased as the dosage of CAE was increased, although
some cements showed a modest increase (gelation) at
intermediate admixture dosages and a decrease only at
higher dosages;
2. The slump of concrete increased and slump loss reduced
as the dosage of CAE increased;
3. With hand mixing, full dispersion of paste was observed
at approximately 0.4 to 0.7% CAE, based on the conversion
from linear viscoelastic to viscous behavior;
4. With high-shear preshear, full dispersion in paste was
observed at approximately 0.13% CAE;
5. Full dispersion in concrete was observed at dosages
approximately 0.11 to 0.13% CAE, based on high slump and
low slump loss;
6. The dosage giving full dispersion in concrete was the
same as the dosage giving full dispersion in paste when paste
was treated using a high-shear pre-shear protocol;
7. Admixture adsorption isotherms indicated that
concretes were fully dispersed at dosages that provided high
slump and low slump loss;
8. Concrete and paste gave similar adsorption responses.
Monolayer adsorption in paste was observed at the same
dosage at which the dynamic rheology behavior converted
from linear viscoelastic to viscous. Monolayer adsorption in
concrete was observed at the same dosage that produced
maximum slump with no slump loss;
9. Concrete slump had an inverse and exponential relationship
with the paste yield stress. Concrete slump had a linear
downward trend on a semi-logarithmic scale with the storage
modulus of paste; and
10. The correspondence between paste and concrete, the
observation of full dispersion at the same admixture dosage
and the correlation between paste rheological parameters
and concrete slump, were only observed when the paste
experiments used a high-shear preshear protocol.
288
ACKNOWLEDGMENTS
The authors are grateful to several organizations for funding this study:
Consolis Technology Oy supported most of the work, the Center for
Advanced Cement Based Materials supported CTC’s preliminary studies,
and SURGE and IMGIP at UIUC provided a fellowship for J. Hidalgo.
Special thanks go to C. Zukoski for allowing use of facilities in the
Colloid Interfacial Laboratory in the Department of Chemical & Biomolecular
Engineering at UIUC, to the Waste Management Research Center at UIUC
for conducting the total organic carbon tests, and to L. Shen in the
Department of Civil and Environmental Engineering at UIUC for determining
the cement surface area. Thanks also to R. Komarek and D. Corcoran for
assistance in the concrete tests. A portion of Table 1 and all of Fig. 3 were
reprinted, with permission, from the Journal of ASTM International
(JAI), V. 3, No. 3, copyright ASTM International, 100 Barr Harbor Drive,
West Conshohocken, PA 19428.
The authors also gratefully acknowledge the following companies for
their contributions: Essroc Inc. (Type I/II cement); W.R. Grace, Inc.
(ADVAFlow, CAE used in preliminary experiments); and Degussa
(Glenium 3200 HES, CAE used in main experiments). The following
companies manufactured the equipment used in this study: Bohlin (CS-10
rheometer); Monarch Industries (Model RLX-3 Type D drum mixer);
Lancaster (30-DP pan mixer) Rigaku (Geigerflex D-Max II X-ray
diffractometer); and Shimadzu (Model VCPN total organic carbon analyzer).
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ACI Materials Journal/May-June 2008