Construction and Building Materials 79 (2015) 65–72

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Construction and Building Materials

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Rheological evaluations of interground and blended cement–limestone

suspensions
Kirk Vance a,⇑, Aashay Arora a, Gaurav Sant b, Narayanan Neithalath a
a
School of Sustainable Engineering and the Built Environment, Arizona State University, Tempe, AZ 85287, United States
b
Laboratory for the Chemistry of Construction Materials (LC2), Department of Civil & Environmental Engineering, University of California, Los Angeles, CA 90095, United States

h i g h l i g h t s

 Rheological effects of limestone in cementitious suspensions brought out.

 Reduction in yield stress with limestone addition; no changes in plastic viscosity.
 Lower apparent yield stress when limestone is interground than blended.
 Viscoelastic storage modulus and apparent yield stress well related.

a r t i c l e i n f o a b s t r a c t

Article history: This paper reports a comparative study of the rheological properties of suspensions composed using
Received 4 August 2014 ordinary portland cement (OPC), interground with, and blended with limestone. Two different inter-
Received in revised form 22 October 2014 ground portland limestone cements (PLCs) and three blended limestone cements were examined. The
Accepted 24 December 2014
blended mixtures were prepared using the same limestone content (by replacement) as the interground
Available online 21 January 2015
mixture, and blended to match the particle size distribution (PSD) of the plain OPC and interground PLCs.
This methodology was used to separate the influence of packing and surface area from the influence of
Keywords:
the limestone incorporation technique (i.e., intergrinding or blending). The results indicate that the inclu-
Rheology
Cement
sion of limestone decreases the yield stress due to reduced van der Waals forces between limestone-to-
Limestone OPC particles, as compared to OPC-to-OPC particle interactions. The plastic viscosity is noted to be inde-
Interground pendent of the limestone replacement level, and dependent solely on the volumetric solid loading and
Fly ash PSD of the solids in the suspension. Intergrinding of limestone is shown to have beneficial effects on
the yield stress compared to PSD-matched OPC–limestone blends, due to coarser OPC fraction in the
interground PLC as compared to the blended mixture. Finally, via oscillatory shear experiments, the
use of a stress plateau identification technique is demonstrated to be an accurate means to identify
the yield stress in cementitious suspensions all suspensions.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
There continues to be interest in the use of fine limestone as a
partial replacement for ordinary portland cement (OPC) in con-
crete. This is due to benefits linked to: low environmental impact,
improved particle packing and filler effects resulting from provi-
sion of additional surface for reactions, and reactions with the alu-
minate phase(s) [1–8]. There are two main strategies for replacing
OPC with limestone: (i) intergrinding the limestone with the clin-
ker in a ball mill (interground portland limestone cement, IPLC), to
⇑ Corresponding author. Tel.: +1 602 663 1778.
E-mail addresses: kevance@asu.edu (K. Vance), aaror24@asu.edu (A. Arora),
gsant@ucla.edu (G. Sant), Narayanan.Neithalath@asu.edu (N. Neithalath).
which the PLCs available in the market fall into, and (ii) mechanical
mixing or blending of the OPC with limestone (blended portland
limestone cement, BPLC). As limestone is a softer material than
the clinker, intergrinding results in limestone particles that are
finer than the OPC particles [9,10], while blending can be tailored
to produce a system where the particle size distributions (PSDs)
of the limestone is similar, finer, or coarser than OPC. Several stud-
ies [11–14] have investigated the influence of limestone on the
rheological performance of cement suspensions. These studies
have investigated the influences of: fineness, superplasticizers,
and limestone content on rheology. However, in these studies
limestone replacement was carried out by intergrinding or using
limestone that is coarser or finer than the OPC. Thus the influence
of limestone in these systems is difficult to discern as it is

http://dx.doi.org/10.1016/j.conbuildmat.2014.12.054
0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
66 K. Vance et al. / Construction and Building Materials 79 (2015) 65–72
confounded with the effects of changes in particle surface area and
particle packing.
The study presented in this paper separates the effects of
changes in particle surface area and particle packing to explore
the effects of limestone incorporation technique: blending versus
intergrinding limestone, on paste rheology. BPLC suspensions are
prepared with limestone which is PSD-matched to OPC to mini-
mize or eliminate the above-mentioned confounding effects. Rhe-
ological characterization of cementitious suspensions is
commonly carried out using strain/stress growth experiments
from which parameters such as the apparent yield stress and plas-
tic viscosity are extracted. The apparent yield stress is indicated by
a non-zero stress at a zero strain rate and the plastic viscosity is a
measure of the increase in strain rate required for a unit increase in
stress. This work applies a new stress plateau identification tech-
nique presented in [15,16] to determine the apparent yield stress,
and extract the plastic viscosity from the linear portion of the shear
rate-shear stress response. In an effort to facilitate discussions on
the material response, which is the focus of the paper, a brief
review of the factors that influence the rheological response of par-
ticulate suspensions, apparent yield stress in particular, follows.
1.1. Apparent yield stress and its determinants in particulate
suspensions
The plastic viscosity of a suspension is strongly influenced by
the solid loading and particle separation, as it is a measure of resis-
tance to flow once it has commenced. The apparent yield stress, on
the other hand, is primarily influenced by particle effects, such as
jamming, particle spacing, surface area and roughness [14,17,18],
and interparticle forces (van der Waals and electrostatic repulsive
forces) [19,20]. The interaction potential between particles in a col-
loidal suspension is governed by DLVO theory, which combines the
effects of van der Waals and electrostatic forces [21,22]. Though
cementitious suspensions have larger particles than would gener-
ally be considered colloidal, DLVO theory is likely still applicable
as the influence of Brownian motion is minimal due to the relative
size of the particles present in the suspension. Electrostatic repul-
sive forces originate from the adsorbed ions in the diffuse portion
of the electric double layer (EDL) [21]. The EDL constitutes an inner
stern layer of tightly held ions that carry a charge that is opposite
to that on the particle surface and the more weakly held ions in the
diffuse outer layer having the same charge as the particle surface.
Electrostatic repulsive effects are proportional to: exp[-
j(r  2a)] [23,24], where r is the distance from the center of the
particle, j is the Debye length, and a is the particle diameter.
Van der Waals forces, on the other hand have been shown to be
proportional to 1/r2, and thus do not decay as rapidly (with dis-
tance) as the electrostatic repulsive force. Further, it is noted that
van der Waals forces between the same materials are always
attractive, while between two different materials they may be
repulsive. Above a certain particle concentration, termed the coag-
ulation limit, the effect of the van der Waals attractive forces dom-
inate over the electrostatic repulsive forces, and it has been shown
that cementitious suspensions are often above this limit [24,25].
Though portland cement grains are polycrystalline, the occurrence
of coagulation in portland cement suspensions combined with the
likelihood that electrostatic effects are repulsive due to similar sur-
Table 1
Chemical composition and physical characteristics of the materials.
Material SiO2 (%) Al2O3 (%)
OPC (ASTM C150) 19.60 4.09
IPLC (ASTM C595) 18.57 3.80
IPLC (ASTM C1157) 18.57 3.84
face charges on cement grains indicate that the net van der Waals
effect is attractive. Thus, above the coagulation limit, as limestone
replaces portland cement in the suspension, the contacts between
OPC particles are decreased, and the influence of limestone–
cement and limestone–limestone contacts become more prevalent,
and interparticle attractive forces would be expected to decrease
along with the apparent yield stress.
2. Experimental program
2.1. Materials
Two as-manufactured IPLCs were used in this study, one conforming to ASTM
C1157 [26] and the other to ASTM C595 [27] with the former being the finer of
the two. The control OPC used in this study was a Type I/II OPC, conforming to ASTM
C150 [28], and was the parent OPC used to generate the three different BPLC mix-
tures. Limestone of four different median particle sizes (0.7, 3, 10, and 15 lm) was
blended with the pure OPC to form the BPLC mixtures. Each of the BPLC mixture has
a particle size distribution that matches either that of the OPC, the ASTM C1157 PLC
or ASTM C595 PLC. The purity of the limestone used is greater than 95% CaCO3. In
the figures and discussions in this paper, the ASTM designation (for example, C 595)
is used for the interground and the corresponding blended systems. For the size
matched BPLC mixtures, the notation ‘=’ is used in the figures to refer to the distri-
bution that the blend is matched to, i.e., OPC + LS = OPC refers to the OPC–limestone
blend which matches the particle size distribution of OPC. The oxide compositions
and physical characteristics of these materials are presented in Table 1.
The particle size distributions (PSDs) of the OPC and the as-obtained IPLCs,
determined using dynamic light scattering, are shown in Fig. 1(a) and (b), respec-
tively. BPLCs were prepared to match the PSDs of the two IPLCs and the parent
OPC, using the same replacement level of OPC by limestone as in the IPLCs (11.1%
by mass; 12.7% by volume, as provided by the supplier). Thus, three blended cement
mixtures were created. A least-squares fitting and error minimization procedure
was adopted to obtain the quantities of limestone of each size required to match
the PSD curves of the OPC or IPLCs. The differential PSDs of these blended systems
as compared to the OPC and the corresponding IPLC systems are presented in
Fig. 1(c). The best possible matches were made by blending chosen amounts of
OPC and the four limestone particle sizes such that the limestone volume fraction
in the blend is 12.7%, by minimizing the least squares error. It is notable that the
blended mixtures were able to reasonably match the size distribution of the OPCs
or the IPLCs except for the case of the C1157 IPLC. The C1157 IPLC is notably finer
than the blend. However, Fig. 1(c) shows that the finer fraction in the C1157 IPLC
and the corresponding BPLC mixture are very similar. Since the limestone is ground
finer than the clinker in the intergrinding process, it is important to match the finer
fraction appropriately to ensure comparability, which has been accomplished here.
2.2. Experimental procedure
The suspensions were prepared at a constant volumetric water-to-solids ratio
(w/s = 1.42), which corresponds to a mass based w/s = 0.45 for OPC suspensions,
and a slightly higher mass-based w/s for blends of limestone due to the lower spe-
cific gravity of this material. A constant volumetric ratio was used as the flow
behavior of concentrated suspensions is influenced by the volume fraction of solids
[29,30]. The specimens were mixed in accordance with ASTM C1738 [31], using a
low shear rate of 5000 RPM for initial mixing, followed by a 30 s mixing period at
a high shear rate of 12,000 RPM, a two minute covered rest period, and finally a
90 s mixing at the high shear rate.
Two different rheological experiments were conducted: one, a typical shear rate
ramp study similar to the one developed in [16], using the parallel plate configura-
tion, and two, a stress growth, low-amplitude oscillatory shear study using a con-
centric cylinder geometry. The typical shear rate ramp study allows for the
determination of yield stress and plastic viscosity of the suspensions while the
stress growth study provides the viscoelastic parameters of the suspension. Both
studies were carried out using a TA Instruments AR 2000EX dynamic shear rheom-
eter, with all rheological parameters (stress, strain rate, storage modulus, and loss
modulus) being extracted using the TA Instruments Trios software package. The
shear rate ramp study was conducted using a 50 mm parallel plate configuration
with the Peltier plate conditioned to a surface temperature of 25 ± 0.1 °C. The upper
surface of the plate geometry was serrated to a depth of 1 mm and the lower surface
of contacting plate (i.e., Peltier cover plate) was serrated to a depth of 0.15 mm to
Fe2O3 (%) CaO (%) MgO (%) SO3 (%) D50 (lm)
3.39 63.21 3.37 3.17 12.4
2.99 63.87 2.93 3.15 11.3
3.11 63.59 3.38 3.23 8.3
 K. Vance et al. / Construction and Building Materials 79 (2015) 65–72
Fig. 1. Particle size distribution (PSD) of (a) OPC and C 1157 and C 595 IPLCs, and (b) limestones used in this study, and (c) differential PSDs of IPLCs (solid lines) compared to
the corresponding BLPCs (dashed lines).
prevent slip at the shearing surface. Slip causes local particle concentration changes
near the shearing surface, potentially resulting in significant underestimation of the
rheological properties [32,33]. The gap between the upper and lower plates was set
to 2 mm, based on prior studies [14,16]. The oscillatory shear experiments were
performed using a concentric cylinder configuration with a constant gap of
1.07 mm between the outer surface of the bob and inner surface of the cylinder.
The contact surfaces were grit-blasted to minimize slip.
The experimental procedure used in the shear rate ramp experiment consists of
a step-up pre-shear to homogenize the sample, followed by a ramp-up and ramp-
down of shear rates. Data acquisition was completed during only the final ramp-
up and ramp-down phases of the study, wherein only data from the down-ramp
portion was used for the extraction of rheological parameters. A graphical overview
of the experimental sequence is presented in Fig. 2. The shear rates used in this
study ranged from 0.005/s-to-100/s, with three points investigated per decade. At
each step, data is collected every second. Each step was terminated once a steady
state has been achieved, as indicated by a difference in torque of less than 5% over
5 consecutive readings, with a maximum step duration of 10 s. The typical duration
of the rheological experiment was 3 min, while the total duration of the experiment
from water addition to completion was approximately 7 min. This experimental
scheme minimizes the experimental duration; as cement hydration is a time-
dependent process, the shortest possible experiment duration is necessary to justify
the assumption that minimal dissolution and hydration occurs during the experi-
ment. The oscillatory shear experiment consisted of a stress growth experiment
beginning at a stress of 0.001 Pa and ending at 50 Pa, at a constant oscillatory fre-
quency of 1 Hz, as this stress range was found to adequately capture the linear vis-
coelastic regime in the suspensions investigated. Oscillatory shear experiments
were conducted so as to minimize the effects of hydration by minimizing the exper-
iment duration. Thus they were conducted over a period of approximately 3 min
with an overall experiment duration from the time of water addition, including
mixing, of approximately 6 min.
Fig. 2. The rheological procedure for shear rate ramp study.
67
Rheological parameters (apparent yield stress and plastic viscosity) for the
shear strain rate growth experiment were extracted using a method presented pre-
viously [16]. The yield stress is determined as the stress value indicated by the
stress plateau, and the plastic viscosity is determined as the slope of the best fit line
over the linear portion of rheological data above a strain rate of 5/s. This method
was shown to be more consistent than using any of the commonly used rheological
models (such as Bingham or Herschel-Bulkley) for cementitious suspensions. A typ-
ical diagram showing the parameter extraction methodology is presented in Fig. 3.
3. Results and discussions
3.1. Rheological response of PSD-matched OPC–limestone blends
This section describes the influence of different levels of PSD-
matched limestone replacement on the rheological behavior of
OPC suspensions. The PSD-matching approach allows the effects
of particle packing and arrangement to be discounted, thereby
facilitating an unbiased investigation of the nature of limestone
in these suspensions. Fig. 4 shows the shear rate-shear stress and
shear rate-apparent viscosity relationships (flow curves) for the
suspensions constituted of OPC and the OPC–limestone blend
(where the cumulative PSD of the blend matches that of the
OPC), where 11.1% of OPC (by mass) is replaced by PSD-matched
limestone.
The rheological performance of OPC suspensions has been
shown to be strongly influenced by solid loading, fineness and
the size distribution of particles [14,17], and the surface interaction
between cement particles. As discussed previously, van der Waals
forces exist between cement particles, and above the coagulation
limit, will dominate over electrostatic repulsive forces [19,34,35].
Aqueous suspensions of calcium carbonate at a high pH have sim-
ilarly been shown to develop large attractive van der Waals forces,
indicative of coagulation [20].
Immediately noticeable from Fig. 4 is the fact that the inclusions
of PSD-matched limestone in an OPC suspension induce negligible
change in the plastic viscosity (as noted by the near-parallel lines),
and a reduction in the apparent yield stress of about the same
magnitude as the volumetric limestone replacement level in the
system. The minimal change in plastic viscosity with the incorpo-
ration of limestone suggests that these surface interaction effects
are less significant in the flow of suspensions once flow has been
initiated. This concept can be intuitively confirmed by considering
the negligible influence of superplasticizers on the plastic viscosity
of portland cement suspensions [36]. The adsorption of superplast-
icizers on the surface of cement particles results in a decrease in
68 K. Vance et al. / Construction and Building Materials 79 (2015) 65–72
Fig. 3. The rheological procedures for shear rate ramp study.
Fig. 4. Representative flow curves for OPC and OPC–limestone suspensions (OPC
replacement by 11.1% by mass of PSD-matched limestone). Solid lines denote the
stress and the dotted lines, the apparent viscosity.
interparticle attractive forces, decreasing the apparent yield stress
but resulting in minimal changes in the plastic viscosity. The slight
influence of superplasticizers on plastic viscosity of OPC suspen-
sions is attributed to the destruction of agglomerations which
releases water and enhances fluidity [11]. Thus, plastic viscosity,
which is a measure of the resistance to flow as the strain rate is
increased, is more heavily influenced by the nature of the suspend-
ing fluid, and the solid fraction and size distribution of the particles
present [17,37]. As the particle size distribution and solid loading
are equivalent in the mixtures considered here, the plastic viscos-
ity is not significantly influenced by the inclusion of limestone.
The apparent yield stress, on the other hand, is a measure of the
resistance to initiate flow, and is thus more strongly influenced by
dispersion and friction forces as well as particle jamming effects.
The rheology of OPC suspensions has been shown to depend signif-
icantly on the interparticle spacing of particles [17], which would
have a direct effect on the magnitude of the forces listed above.
Increasing the spacing by the inclusion of a higher volume of water
or a reduction in surface area more significantly decreases the elec-
trostatic repulsive forces (as compared to van der Waals dispersion
forces), thereby decreasing the interparticle attractive forces
between cement particles, and resulting in a reduction in the
apparent yield stress. Further, it is noted the plastic viscosity
remains relatively constant despite OPC replacement by limestone,
supporting the idea that interparticle spacing is unchanged, and
thus surface area remains relatively constant. Thus, it is proposed
that, as PSD-matched limestone replaces OPC in the suspension,
the magnitude of the van der Waals forces between limestone
and cement are lower than those between the cement particles.
The replacement of portland cement by limestone, which reduces
the particle contacts between cement grains1, thus acts to decrease
the net interparticle attractive forces in the suspension, thereby
decreasing the apparent yield stress.
To further investigate the influence limestone replacement on
the rheological properties of portland cement suspensions, a study
was performed at additional PSD-matched limestone contents of
23% and 33% by volume (20% and 30% by mass) while maintaining
the same volumetric water-to-solids ratio of 1.42. Fig. 5(a) depicts
the apparent yield stress and plastic viscosity of these suspensions
as a function of the volumetric PSD-matched limestone replace-
ment level. Noted from this figure is a similar influence as seen
in Fig. 4, with a constant plastic viscosity regardless of the lime-
stone content (within the range of replacement levels studied)
and a continuing decrease in apparent yield stress as the limestone
content is increased (attributed to a reduction in cement–cement
contacts and an increase in cement–limestone contacts which have
lower associated interparticle forces). This supports the idea that
plastic viscosity is more heavily influenced by the particle size dis-
tribution and the surface area of particles present in the suspen-
sion. Even as more limestone replaces cement in the suspension,
the composite PSD and the specific surface areas remain relatively
unchanged, resulting in unchanged plastic viscosity. The apparent
yield stress, on the other hand, is more strongly influenced by
interparticle forces. These results support the discussions above,
wherein the van der Waals forces between adjacent limestone
and cement particles are significantly lower than those between
cement particles, and thus increasing the limestone content in
the suspension at a constant solid loading with an unchanged
PSD results in a continued reduction in interparticle forces, and
subsequent reductions in the apparent yield stress.
To investigate these effects, the yield stress was normalized by
the mass of cement in the suspension in Fig. 5(b) and plotted as a
function of the volumetric limestone replacement ratio. The nor-
1
A computer simulation on a 200 lm  200 lm  200 lm 3D representative
volume element packed with particles and water, corresponding to the chosen (w/s)V,
showed that the interparticle spacing was unchanged due to the incorporation of
size-matched limestone. Further, when 12.7% of cement is replaced by limestone,
cement–cement particle contacts reduce to 75.25% (from 100% for a pure OPC
system), with 23.06% being cement–limestone particle contacts and 1.69% being
limestone–limestone particle contacts.
 K. Vance et al. / Construction and Building Materials 79 (2015) 65–72
Fig. 5. Influence of the content of PSD-matched limestone on determined rheological properties of the suspension.
malized yield stress is found to remain constant at low limestone
contents, but increases as the replacement level increases beyond
a certain value. At low OPC replacement levels, OPC–OPC and
OPC–limestone particle contacts would likely dominate. The
unchanged normalized yield stresses at lower replacement levels
supports the idea that the repulsive van der Waals forces between
limestone and OPC particles is likely negligible as compared to the
attractive force between OPC particles. However, as the limestone
content increases further, limestone–limestone contacts become
prevalent. It has been shown that suspensions of limestone result
in similar van der Waals attractive forces as suspensions of cement
[20], and when the limestone–limestone contacts in the suspen-
sion become more prevalent, the normalized apparent yield stress
increases. It is likely, that if the limestone content were increased
further, an inflection point in the continuation of Fig. 5(a) would
be found, as increasing limestone–limestone contacts as compared
to limestone–OPC contacts would eventually result in an increase
in the apparent yield stress.
3.2. Comparing the rheological parameters of IPLC and the
corresponding BPLC suspensions
3.2.1. Yield stress and plastic viscosity
Rheological studies were performed on the IPLCs and PSD-
matched BPLCs as presented in Section 2. The blends were propor-
tioned to match the PSD of the parent OPC and both IPLCs (Fig. 1)
with the same volumetric OPC replacement level as the IPLCs
(12.7% by volume or 11.1% by mass). Fig. 6 shows the rheological
parameters of the IPLCs and the corresponding BPLCs.
The first two observations can be explained as follows. The con-
stant plastic viscosity across all suspensions except the C 1157 IPLC
is due to the similar PSDs and specific surface areas. As discussed
previously, similar PSDs and specific surface areas yield similar
plastic viscosities if all other experimental variables are held con-
stant, due to the constant water film thicknesses around the parti-
cles in these suspensions. Achieving a reasonable PSD match with
the finer C1157 IPLC was not possible with the sizes of limestone
used in this study, as mentioned in Section 2. The finer interground
mixture has a larger surface area than the corresponding blended
mixture which is coarser, resulting in a decrease in water film
thickness and subsequent increase in plastic viscosity. The
increased fineness also decreases particle separation, which
increases the interparticle attractive forces, and consequently the
apparent yield stress of the C1157 IPLC suspension as compared
to the other suspensions. These results are similar to the observa-
69
Fig. 6. Yield stress and plastic viscosity of the OPC, IPLC, and the corresponding
BPLC suspensions Several important observations can be made from Fig. 6: (i) the
plastic viscosity is approximately constant regardless of whether the mixture is
blended or interground, with the exception of the C1157 IPLC suspension, (ii) the
C1157 IPLC suspension shows both higher apparent yield stress and plastic
viscosity, and (iii) the C595 BPLC suspension has a higher apparent yield stress as
compared to the corresponding interground PLC suspension.
tions on the influence of the fineness of limestone powder on OPC
suspension rheology which has been reported in detail in [14].
The third observation, i.e., of the C595 IPLC suspension having a
lower apparent yield stress as compared to the equivalent blended
suspension, can be explained by considering the relative size distri-
butions of limestone and OPC in the blend. The similarities in PSDs
of the blended and the interground systems (Fig. 1(c)) combined
with similar volume fractions of limestone leads to the expectation
that the apparent yield stress and plastic viscosity in these suspen-
sions would be equivalent. However, intergrinding limestone with
portland cement clinker will result in a finer limestone phase and a
coarser cement phase in the blended cement due to the relative
softness of limestone as compared to portland cement clinker [9].
The results from the PSD-matched OPC–limestone blends in Sec-
tion 3.1 leads to the inference that the interparticle attractive
forces between limestone and cement are lower than those
between the cement grains, resulting in a reduction in yield stress
as PSD-matched limestone replaces OPC. Further, at the same
replacement level it is noted that the C595 IPLC is finer than the
OPC-equivalent OPC–limestone blend as indicted in Fig. 1c, which
would be expected to increase the yield stress of the C595 IPLC sus-
pension as noted in Fig. 6. Similarly, as both the C595 IPLC and the
corresponding BPLC have comparable PSDs, it would be expected
70 K. Vance et al. / Construction and Building Materials 79 (2015) 65–72
Fig. 7. Relationship between shear stress and storage (solid lines) or loss (dashed lines) moduli of suspensions: (a) pure OPC and the OPC–limestone blend with same PSD as
OPC; (b) C595 IPLC and BPLC; and (c) C1157 IPLC and BPLC.
that the yield stress of these two suspensions would be equivalent,
however they are noted to be different. The primary difference
between the blended and interground systems, as discussed previ-
ously, is the particle size distributions of the limestone and OPC in
the mixture. Thus, the reduction in yield stress in the C595 IPLC
suspension as compared to the corresponding BPLC suspension is
likely attributed to the coarser cement particles in the IPLC mix-
ture. This coarser OPC fraction would result in a decrease in the
cement particle contacts as compared to the equivalent blended
mixture, which subsequently reduces the interparticle attractive
forces and decreases the apparent yield stress.
3.2.2. Observations from oscillatory shear stress ramp experiments
Small amplitude oscillatory stress growth experiments were
performed on suspensions of IPLC and BPLC suspensions. Oscilla-
tory stress growth experiments are used to extract the storage
and loss moduli, which are the elastic and viscous components of
a viscoelastic material respectively, as a function of applied stress.
The typical shape of the moduli-shear stress relationships is a hor-
izontal modulus plateau, followed by a significant reduction over a
rather small range of stress, indicative of structural breakdown
[38], and followed by a plateau at a lower modulus level. Fig. 7
shows the relationships between the shear stress and storage/loss
moduli for the OPC, the IPLC, and the corresponding BPLC
suspensions.
Comparing Fig. 7(a)–(c), it is noted that the trends in the storage
and loss moduli of the suspensions in the linear viscoelastic regime
(i.e., defined as the regime over which the moduli are independent
of stress [39], i.e., see the plateau region) can be expressed as
OPC < C595 < C1157, for both the as-obtained cements (OPC and
the IPLCs), and the PSD-matched BPLCs. The increase in moduli
corresponds with an increase in the fineness of the cement or the
blend, where the OPC is least fine and the C1157 PLC is the finest
as indicated in the PSD curves presented in Fig. 1. Further, this
trend is consistent with the apparent yield stress results shown
in Fig. 6.
To allow for further discussions on the viscoelastic nature of
these suspensions, it is useful to examine the viscoelastic phase
angle d, defined as:
G00
¼ tan d
G0
The phase angle represents the ratio of the viscous to elastic
moduli of the material, with a lower value representing a more
solid, or elastic behavior, and a higher value indicating a more
liquid or viscous response. Thus, a phase angle of 1 would repre-
sent a Newtonian fluid and a phase angle of 0 would represent a
perfectly elastic solid. The elastic portion of the response is domi-
nated by interparticle contacts and interparticle forces. Fig. 8
shows the phase angles for all the suspensions evaluated here,
and it can be noticed that the trend is consistent with the observa-
tions in Fig. 6, with the C1157 IPLC suspension showing the lowest
phase angle, and the PSD-matched OPC–limestone blend equiva-
lent to the pure OPC showing the highest. Comparing the pure
OPC suspension to the PSD-matched blend corresponding to OPC,
there is a noted increase in the phase angle for the blended suspen-
sion. As the PSDs are similar and solid loading is the same in both
these suspensions, this effect can be attributed solely to changes in
the interparticle forces in these mixtures. This result also follows
the inferences from the discussions on limestone–cement disper-
sion forces presented earlier, where the inclusion of a relatively
small fraction of PSD-matched limestone results in a more fluid
behavior, attributed to a reduction in interparticle attractive forces
in the particle network due to lower limestone–cement dispersion
forces. The lower phase angle in the C595 BPLC suspension as com-
pared to the corresponding IPLC suspension can similarly be attrib-
uted to the particle sizes of cement and limestone as discussed
previously. Finally, the lower phase angle in the C1157 IPLC sus-
pension as compared to all other suspensions can be attributed
to the finer particle size distribution in this suspension, which
would act to decrease particle spacing and increase particle con-
tacts thereby increasing the interparticle attractive forces and
allowing the suspension to behave in a more solid-like manner.
Comparisons of the viscoelastic response to the flow response
from the strain growth experiments indicate a very strong correla-
tion between the storage modulus and the yield stress as indicated
ð1Þ
Fig. 8. Viscoelastic phase angle (d) for investigated suspensions.
 K. Vance et al. / Construction and Building Materials 79 (2015) 65–72
Fig. 9. (a) Relationship between yield stress and storage modulus in the linear viscoelastic regime, and (b) effect of median particle size on yield stress and storage modulus.
in Fig. 9(a). This relationship is one that is expected, as a higher
storage modulus would indicate a more elastic behavior, which
in turn indicates a more structured network with higher interpar-
ticle attractive forces, and consequently a higher apparent yield
stress. The good correlation between the storage modulus and
yield stress also confirms the accuracy of the determination of
apparent yield stress from the plateau of shear stress-shear rate
relationship at lower shear rates rather than the use of simplified
models [16].
Fig. 9(b) illustrates the influence of median particle size (D50) on
both the storage modulus and yield stress of the suspensions. A rel-
atively strong correlation is noted in this figure; however there is
some degree of scatter. As the median particle size increases, the
water film thickness on the surface of the suspended particles
would increase, resulting in increased particle separation and a
reduction in the interparticle attractive forces. These results are
consistent with those in [14,17], which indicate that the rheologi-
cal properties of suspensions are strongly influenced by the sizes of
the suspended particles. However, it needs to be remembered that
the viscoelastic and yield stress response are also influenced by the
particle interactions in these suspensions. Thus, the scatter in this
figure is likely attributed to changes in interparticle forces in the
particle network resulting from the replacement of OPC with lime-
stone. As described in detail previously through deductions from
experimental observations, limestone–cement particle interaction
effects have been illustrated to be lower than cement–cement
interaction, which justifies the changes in the yield stress and vis-
coelastic response of these binder systems despite comparable
PSDs.
4. Conclusions
This paper has presented the rheological influence of limestone
in interground and blended OPC suspensions. OPC–limestone
blends were prepared by using limestone particles of four different
median sizes to ensure that the blends have the same PSDs as the
parent OPC or the IPLCs. This helped eliminate the effects associ-
ated with the influences of particle packing and surface areas. With
increasing amounts of limestone in the blends, yet keeping the
composite PSD the same as that of the parent OPC, the apparent
yield stress was found to decrease because of the increasing inter-
particle spacing between the cement grains. This indicates that the
van der Waals forces between limestone and cement are signifi-
cantly lower in magnitude than those between the cement parti-
cles. The determination of viscoelastic parameters of the
suspensions (storage and loss moduli, and the phase angle) also
validated these observations. The plastic viscosity on the other
hand remained invariant with limestone content, reinforcing its
71
primary dependence on the component volume fractions and size
distribution of the particles. It is further noted that interground
PLC suspensions demonstrated lower apparent yield stresses than
the blended suspensions of the same PSD and limestone replace-
ment ratio at the levels studied. This is a result of the softer lime-
stone particles being ground finer than the clinker in the
interground mixtures and consequently the coarser OPC particles
resulting in reduced cement particle contacts (and thus reduced
dispersion forces). The finer IPLC system in this study showed
the opposite behavior as above, a phenomena attributed the finer
PSD of the IPLC suspension as compared to the size matched BPLC
suspension. A very good correlation was obtained between the vis-
coelastic storage modulus and the apparent yield stress, while both
the storage modulus and yield stress showed reasonable inverse
correlations with the median particle size.
Acknowledgements
The authors gratefully acknowledge the National Science Foun-
dation (CMMI: 1068985) and Arizona State University for the sup-
port of this research. The materials for this research were provided
by Lehigh Cement and Omya A.G. and these corporations are
acknowledged. K.V. also acknowledges the Dean’s Fellowship from
the Ira A. Fulton Schools of Engineering at Arizona State University
(ASU). This research was conducted in the Laboratory for the Sci-
ence of Sustainable Infrastructural Materials (LS-SIM) at ASU and
the authors gratefully acknowledge the support that has made this
laboratory possible. The contents of this paper reflect the views of
the authors who are responsible for the facts and accuracy of the
data presented herein, and do not necessarily reflect the views
and policies of the funding agency, nor do the contents constitute
a standard, specification, or a regulation.
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