Construction and Building Materials 71 (2014) 26–34

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Influences of limestone particle size distributions and contents

on blended cement properties
Yaniv Knop a, Alva Peled a,⇑, Ronen Cohen b
a
Structural Engineering Department, Ben-Gurion University of the Negev, Beer-Sheva, Israel
b
Nesher Cement Enterprises LTD, Ramla, Israel

h i g h l i g h t s

 We developed limestone cement with high packing density to maximize binder properties.
 Limestone powders with three main particle diameters were examined.
 Combinations of limestone powders with several different particle sizes were studied.
 Increasing surface area and packing density improve blended cement performances.
 Blended cement with a combination of several particle sizes performed the best.

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

Article history: Limestone cement with high packing density was developed to maximize binder properties in spite of
Received 3 April 2014 increased limestone contents. Limestone powders with three main particle diameters relative to the clin-
Received in revised form 30 June 2014 ker particles were used. Cements with a single-size limestone particle and with combinations of several
Accepted 4 August 2014
particle sizes were compared. It was concluded that the replacement of an active material with an inert
Available online 7 September 2014
additive can improve cement paste performances by increasing the surface area and the packing density
of the cement-based particles, mainly when limestone powders with a combination of several different
Keywords:
particle size distributions were used due to increased packing density.
Hydration
Particle size distribution
Ó 2014 Elsevier Ltd. All rights reserved.
Blended cement
CaCO3
Sustainability
Specific surface

1. Introduction
Due to environmental and energy efficiency concerns, there is
growing interest in the development of a blended Portland cement
in which the amount of clinker is reduced and partially replaced
with mineral additives. There are three principal motivators
behind these efforts: (1) ecological benefits, as a result of lower
CO2 emissions to the atmosphere, (2) economic benefits, since
reduced clinker cement is cheaper to produce, and (3) scientific/
technological benefits, based on improved cement and concrete
performance. There are two main types of mineral additives com-
monly used: (1) pozzolanic additives such as fly ash, slag, and
⇑ Corresponding author. Address: Structural Engineering Department, Ben-Guri-
on University of the Negev, P.O. Box 653, Beer-Sheva 84105, Israel. Tel.: +972 8 647
9672; fax: +972 8 647 9670.
E-mail addresses: yaniv.knop@gmail.com (Y. Knop), alvapeled@bgu.ac.il (A.
Peled), ronenc@nesher.co.il (R. Cohen).
metakaolin [1–3] and (2) materials which are not considered poz-
zolanic, generally having low reactivity with cement minerals. Of
the latter type, limestone is one of the most attractive additives
because it is considered natural, available, and economical. Several
studies have reported that cement blended with limestone had
improved initial compressive strengths with lower setting times
compared to the original cement, i.e., without added limestone
[4–6]. The addition of fine inert limestone powder, whose surface
area was greater than that of the clinker, increased the hydration
rate at early age and the generated heat of hydration [5]. However,
the final strength of the blended cement after 28 days was less
than that of the original cement paste.
Cement properties have been explained by the effect of packing
density, which is defined as the ratio between the solid phase vol-
ume and the total volume of the system (Fig. 1). The inclusion in
the system of particles with improved particle size gradation con-
fers on it increased packing density and, thus, decreased porosity,
as was also described by the linear packing density model of grain

http://dx.doi.org/10.1016/j.conbuildmat.2014.08.004
0950-0618/Ó 2014 Elsevier Ltd. All rights reserved.
 Y. Knop et al. / Construction and Building Materials 71 (2014) 26–34
Fig. 1. Packing density theory (hierarchical approach) [8].
mixtures by Stovall et al. [7]. Fig. 1a schematically illustrates the
packing density of a system in which the presence of small parti-
cles reduces the unoccupied spaces between the larger particles
(A, B, C, and D) [8]. Fig. 1b and c shows that the space between
the smaller particles is filled by even smaller particles (i.e., a hier-
archical approach).
The addition of fine limestone powder as clinker replacement
has also been shown to increase the number of nucleation centers,
an outcome elicited by its high surface area [5]. The greater the
number of nucleation centers during the hydration process, the
higher its hydration rate and early age strength. According to
Voglis et al. [9], to obtain a limestone–cement blend of similar
strength to that of cement alone (without limestone) at day 28
after blending, the surface area of the limestone cement must be
higher than that of the cement. Kumar et al. [10,11] showed that
an increase in the cement fineness, filler fineness, or filler content
acts to increase chemical reactions. Oey et al. [12] also showed the
influence of powder addition (limestone and quartz) on the solid
surface area of the system by an area multiplier (AM) and its effect
on the reaction rate.
Although limestone is considered an inert additive, there is sub-
stantial evidence that it is not completely inert, and during the
hydration process, additional products are formed by the reaction
of the limestone and the C3A phase [13–16]. Several researchers
have reported that partial replacement of clinker with mineral
additives influenced the flow and workability of fresh cement
paste [17–21]. The flow behavior of clinker with mineral additives
is affected by several factors such as the particle shape, reactivity
of the additives, the content, and the packing density of the parti-
cles. In systems with higher packing density, less water is trapped
between the particles, making more water available to lubricate
the particles, increasing the flow and workability of the fresh
cement paste.
Our work has developed blended limestone cement with higher
packing density and optimal surface area related to the original
cement to maximize the properties of the binder. The limestone
particles were grinned separately and then added to the original
cement. Limestone powders with several different particle sizes
were used to partially replace the original cement. Single particle
size distributions of limestone were compared with systems con-
taining multiple combinations of limestone particle size distribu-
tions. The amount of water required to obtain a hydraulic binder
having a normal consistency and the hydration degree were exam-
ined using penetration depth vs. time measurements until reach-
ing final setting. Also compressive strength measurements,
scanning electron microscopy, and Rietveld quantitative phase
analysis of X-ray diffraction were used to examine the blended
cement properties.
27
2. Material and methods
CEM I 52.5 R was partially replaced with limestone powders (>99.8% CaCO3)
with varying particle size distributions. The chemical composition of the original
cement is presented in Table 1. Three different limestone powders representing
several particle diameters—smaller than, larger than, or similarly sized to the origi-
nal CEM I with a mean particle size of 17 lm—were tested. The limestone powders
with the smaller and similarly sized particles to the original cement were fractions
of the same source, while the limestone with larger size was from a different source.
However, the purity and the density of the limestone powders were similar. Two
different powder systems were prepared and investigated:
(i) Single-particle-size distribution system: The original cement was partially
replaced with limestone with a single-particle-size distribution—either
smaller than, larger than, or similarly sized to the cement particle. Cement
replacement effects were investigated using several limestone–cement
mixtures in which the limestone powder comprised 5%, 10%, 20%, or 30%
of the mixture (by mass).
(ii) Combined-particle-size distribution system: The original cement was par-
tially replaced with limestone powder containing a combination of particles
that were larger than and smaller than the cement particles. Several mix-
tures were tested, in which the ratio of large to small limestone particles
was varied (1/4, 3/2, or 4/1). All mixtures contained only 5% limestone.
Several testing methods were used to study the properties of the powders, the
fresh cement pastes, and the hardened cement pastes.
2.1. Powders
Surface area and particle size distribution (PSD) were examined for the pow-
ders. The surface area of each individual powder was determined using the BET
technique with N2. Cement and limestone powder surface areas were calculated
by multiplying the cumulative relative weight of each powder by the surface area
of the individual component in the powder mixture. Particle size distribution was
determined by laser diffraction scattering (CSI-100, Ankersmid).
2.2. Cement pastes
The workability of each cement paste was determined based on normal consis-
tency. Each cement powder—blended or original—was mixed with the amount of
water needed to obtain a normal consistency according to EN 196/3. After each
sample (i.e., original cement or original cement + limestone) was mixed to normal
consistency according to the standard, the sample was placed in water at
20 ± 1 °C, and the penetration depth was measured until the final setting time
was obtained by an automatic Vicat Needle Apparatus (Toni Technik). The bulk den-
sity of the different fresh cement pastes was measured following Wong et al. [19].
For this measurement, the original cement and blended cement pastes with 20%
limestone composed of three different particle sizes (53 lm, 25 lm, and 3 lm)
were prepared all to normal consistency. The weight of three samples of each paste
type was measured in a container with a volume of 250 ml. First the container was
half filled with the fresh paste and then was compacted using a vibration table for
1 min. After the compaction of the first layer, the container was completely filled
and compacted for another minute. The average bulk density value of each paste
type was then calculated.
2.3. Mortar hardening
Following EN 196-1 to evaluate compressive strengths, the cement pastes dis-
cussed above were mixed with standard sand with a maximum particle size of
1.60 mm and water to obtain a water:powder:sand weight proportion of 0.5:1:3,
such that the cementitious material (original cement + limestone powder) content
was 450 g. The specimens were mixed and cast in molds measuring
40  40  160 mm. After curing the specimens for 24 h at 20 ± 1 °C, they were
demolded and immersed in water at 20 ± 1 °C until the compressive strength was
tested. The compressive strength of each sample was measured in a press (Toni
Technik) 1 d and 28 d after casting, and each sample’s strength was based on an
average of six specimens.
Fragments of the hardened mortar blends obtained after testing the compres-
sive strengths were prepared for microstructure mineral content analysis and
image analysis. To that end, the fragments were immersed in acetone for 1 h to
remove the water and then kept in a stove for 120 min at 60 °C. Immediately after
this procedure, the specimens were vacuum impregnated with low viscosity epoxy.
After 24 h, the samples were ground with # 220, # 500, # 1200, and # 2400 sand-
papers, after which they were polished with 3-lm alumina oxide paste on a lap
wheel.
The microstructures of these polished specimens were observed using a TES-
CAN VEGA3 scanning electron microscope (SEM). Energy dispersive X-ray spectros-
copy (EDX) was used to provide elemental identification and compositional
28 Y. Knop et al. / Construction and Building Materials 71 (2014) 26–34

Table 1
Chemical composition of the original cement.

Component CaO SiO2 Al2O3 Fe2O3 MgO TiO2 K2O Na2O P 2 O5 Mn2O3 SO3
% 65.07 18.96 4.5 2.46 1.16 0.36 0.33 0.21 0.32 0.30 2.86

information. Rietveld quantitative phase analysis of X-ray diffractions was used to

determine the mineral content of the cement paste and to calculate the hydration
degree of each sample, including the original cement and the cement mixed with
limestone. XRD analysis was performed on an ARL X’TRA X-ray diffractometer (Cu
Ka radiation, 45 kV, 40 mA) in a scanning range of 7–53° in 2h at an internal of
0.020°.

3. Results and discussion

3.1. Physical properties of the powders

The PSD and the surface area of the original cement and of lime- Fig. 2. Particle size distribution (PSD) of the tested powders (cement and
stone powders are given in Table 2. limestone).
Fig. 2 shows the particle size as a function of the cumulative
volume of the solid for the three tested limestone powders and
the cement. The mean particle size of each powder, based on the
PSD analysis, was determined by the volume of the particles. In
Fig. 2, the mean size of each limestone powder and of the original
cement are represented by the dashed lines. The three different
limestone sizes used had mean particle sizes of 53 lm, 25 lm,
and 3 lm, each of which is signified by CCX, such that X stands
for the particle size, e.g., CC3 is the limestone powder with mean
particle size 3 lm. Note that for the limestone powder with the
largest mean particle size of 53 lm, only a portion of its particles
were larger than (measuring from 45 lm to 100 lm) those of the
original cement. In the case of the limestone powder with the
smallest mean particle size (3 lm), most of its particles were smal-
ler than those of the original cement.
The ratio between the surface area of each blended powder
(limestone + cement) and of the original cement as a function of
the percent of original cement replaced with the limestone is
shown in Fig. 3a for the different limestone powders (e.g., CC3 lm,
CC25 lm, and CC53 lm). A scaling factor (AM) was introduced by
Kumar et al. [10] to describe the relative change in the solid surface
area induced by the filler addition in comparison to the surface
area provided by unit mass of cement. The influence of the lime-
stone replacement content on the solid surface area is shown in
Fig. 3b by using an area multiplier (AM, unitless). In both cases,
the surface area is strongly correlated with that of the respective
limestone powder used in the mixture for the three tested systems.
The finest limestone powder (CC3 lm) observed the greatest AM
factor, which exhibited the highest increase in the AM factor when
increasing its content in the blended cement.
Fig. 3. (a) Surface area of the tested powders (cement and limestone) and (b) the
correlation between the area multiplier to the limestone content in the blended
3.2. Water amounts for normal consistency cement and subsequent
cement.
packing density

Water was added to the blended cement powders until normal pare normal consistency cement and the packing density is given
consistency was obtained based on EN 196/3. Water demand is in Eq. (1) [22], taking into consideration the specific density and
affected by several factors such as particle shape, particle surface weight of the examined powder.
area, density of the material, and the packing density of the parti-
1
cles. The correlation between the amount of water required to pre- ;¼ ð1Þ
1 þ qP wp

Table 2 where ; is the packing density, W is the water required to mix

Mean particle size and surface area of the tested powders. cement paste of normal consistency, p is the powder weight, and
Type Cement CC53 lm CC25 lm CC3 lm
qp is the specific density of the dry powder.
When particles of the same material with similar shape and
Average size, lm 17.02 53.40 25.78 2.99
density were used, differences in particle size distribution and
Surface area, m2/g 1.533 0.390 1.371 6.222
the corresponding voids between the particles meant that mixing
 Y. Knop et al. / Construction and Building Materials 71 (2014) 26–34
each cement paste system to normal consistency required a differ-
ent amount of water [19–20], i.e., the amount of water required is
indicative of the total volume of the unoccupied spaces between
the particles, or the packing density of the particles.
Fig. 4 illustrates the relationship between the amounts of water
required to achieve normal consistency of the blended cements
with the different limestone contents for each particle size relative
to the original cement (without added limestone). For cement
blends with limestone particles larger (CC53 lm) than those of
the original cement, the amount of water needed for normal con-
sistency decreased as the limestone content was increased. How-
ever, for systems with limestone particles smaller (CC3 lm) than
those of the cement, water amounts increased with increases in
the limestone content. Reduction in water demand reveals greater
packing density. The calculated packing density values based on
Eq. (1) of the blended cements with the different limestone con-
tents for each particle size are presented in Fig. 5. 0% represents
the result of the original cement. This figure clearly shows an
increase in the packing density of the blended powder cement sys-
tems with the larger limestone particles and lower surface area
compared with that of the original cement. In contrast, the packing
density of cement systems blended with limestone containing
smaller particles and higher surface area decreased, mainly for
the high content of limestone (above 20% replacement). Finally,
the packing density of cement systems blended with limestone,
whose surface area was similar to that of the original cement
(CC25 lm), also increased but to a lesser extent than that of the
large particle sample, mainly for blended cement with 30% lime-
stone content. This trend is supported by the bulk density of the
fresh blended cement pastes with 20% limestone content (Fig. 6).
The bulk density is presented in percentages relative to the bulk
Fig. 4. Amount of water required to prepare blended cement pastes at normal
consistency with different limestone particle sizes and replacement contents.
Fig. 5. Calculated packing density based on Eq. (1) for the different limestone
particles and contents.
29
Fig. 6. Bulk density of the fresh blended cement pastes with 20% of limestone
having different particle sizes.
density of the original cement for the three blended cements with
the different limestone sizes. The figure clearly shows an increase
in the bulk density of the blended cement systems with the larger
limestone particles and lower surface area, indicating greater pack-
ing density for the large particle system.
3.3. Penetration depths vs. time
The setting and hardening of cement is a continuous process.
The penetration depths at time intervals were measured until
reaching the final setting time according to EN 196/3, indicating
the hydration rates of the different systems. The results are pre-
sented separately for the blended cement systems containing lime-
stone with one-particle-size distribution and for the combined-
particle-size systems.
3.3.1. Blended cement systems—one-particle-size distribution
The curves of penetration depths vs. time up to final setting of
the original cement system and of the three cement systems
blended with limestone particles with sizes of 53 lm, 25 lm, or
3 lm for replacement contents of 5%, 10%, 20%, or 30% by weight
are presented in Fig. 7. In general, the size of the particles of the
limestone powder markedly affected the time values needed to
obtain penetration depths up to the final setting of the blended
cement pastes relative to that of the original cement paste.
Cements blended with limestone whose particles were larger
(CC53 lm) than those of the original cement exhibited longer time
values at similar penetration depths, i.e., slower hydration rates,
which grew with increases in limestone powder content, compared
to that of the original cement for all limestone replacement con-
tents. Cement replacement with limestone with a surface area sim-
ilar to that of the cement (CC25 lm) presented similar penetration
depths vs. time behavior for all limestone contents i.e., the rate of
hydration was similar regardless of whether limestone was added
(Fig. 7b). Replacing the cement with limestone containing smaller
particle sizes (CC3 lm, i.e., with larger surface area) than that of
the original cement led to shorter time values for penetration
depths up to final setting, i.e., faster hydration rates than that of
the original cement (Fig. 7c). The time to reach a specific penetra-
tion depth of 20 mm for blended cement with limestone particles
with sizes of 53 lm, 25 lm, or 3 lm for replacement contents of
5%, 10%, 20%, and 30% is presented in Fig. 8. 0% represents the ori-
ginal cement without limestone. An increase in the time required
to reach a penetration depth of 20 mm is clearly observed as the
limestone content increases for the largest limestone particles
(CC53 lm), while shorter times are observed for the smallest lime-
stone particles (CC3 lm) as the limestone content increased. No
significant difference in the time required to reach a penetration
depth of 20 mm is observed for limestone with surface area similar
to that of the cement (CC25 lm) as limestone content increased.
The effect of limestone particle size on hydration rates can be
attributed to the increased or decreased number of nucleation
30 Y. Knop et al. / Construction and Building Materials 71 (2014) 26–34
Fig. 7. Penetration depth vs. time behavior of original cement and blended cements
with 5%, 10%, 20%, and 30% wt. limestone with particle size of: (a) CC53 lm (b)
CC25 lm, and (c) CC3 lm.
Fig. 8. The time to reach 20 mm penetration depth of blended cements with
limestone particle sizes of CC3 lm, CC25 lm, and CC53 lm limestone contents of
5%, 10%, 20%, and 30% by weight. 0% represents the original cement.
centers [5,6,12]. Inan et al. [23] observed a layer of calcium–sili-
cate–hydrates (C–S–H) around the surface of the limestone particle
despite the inactive character of limestone, which does not react
with water. The presence of this layer indicates that C–S–H grows
not only around the clinker particle, as expected, but also around
the limestone particle. Similar observations were also reported
by Kumar et al. [10] that examined a variety of mixtures composed
of different cements. These observations demonstrate that the
limestone particles provide additional nucleation centers. Thus,
partial replacement of the cement with limestone containing par-
ticles with larger surface areas compared to those of the original
cement particles produced a blend with a greater number of nucle-
ation centers than in the original cement. Because the hydration
products also develop on the limestone particles and not only on
the cement particles, the subsequent hydration rate of such a blend
is high. In contrast, when the limestone in the cement–limestone
blend was composed of particles with smaller surface areas than
those of original cement particles, the number of nucleation cen-
ters—and subsequently, the hydration rate—decreased.
As discussed in Section 3.1, the increase in limestone content
led to an increase in the surface areas of the fine limestone blended
cement powders (Fig. 3). Therefore, for the cement blended with 3-
lm limestone particles (CC3 lm), i.e., the smallest investigated
particle with the highest surface area, faster hydration rates were
observed compared to the original cement for all replacement con-
tents, as expected (Fig. 7c). However, for this fine particle system,
no straightforward correlation was observed between the surface
areas of the different limestone content systems and the setting
process, as can clearly be seen in Figs. 7c and 8. Similar behaviors
of penetration depth vs. time were observed for the cement
blended with either 5% or 10% limestone, i.e., similar setting rates
despite the greater surface area of the 10% vs. the 5% limestone
blended cement (Fig. 3). This trend is clearly noticed in Fig. 8, pre-
senting similar time values of 166 and 168 min for 5% and 10% con-
tents, respectively, to reach a 20-mm penetration depth. A similar
trend was also observed when comparing the 20% with the 30%
blended cement systems (Figs. 7c and 8).
On the other hand, fine limestone particles can agglomerate as
presented in Fig. 9. This figure presents a SEM image of mortar
made of blended cement with the small-particle limestone
(CC3 lm). Agglomeration, a result of interparticle interaction, cre-
ated a massive, ‘‘particle’’ whose size was over 100 lm. The effect
of agglomeration is expected to be dependent on the replacement
content of the original cement with limestone having fine particles.
Replacement of a small percentage of original cement with fine
limestone particles is expected to cause, if any, only a local level
Sand parcle
Limestone
agglomeraon
Fig. 9. SEM image of agglomeration of limestone particles near a sand particle of
mortar with blended cement with the smallest limestone particles (CC3 lm) using
EDS analysis.
 Y. Knop et al. / Construction and Building Materials 71 (2014) 26–34
effect because of the dispersion of the limestone in the original
cement. However, by the increased content of limestone having
fine particles, agglomeration is expected to be more dominant.
Thus, by increasing the content of fine particles above a certain
percentage, the packing density decreased because of the agglom-
eration effect, and this in turn decreased the effective surface area.
It should be remembered that with these very fine powder sys-
tems, the amount of water needed to mix a paste of normal consis-
tency is increased with the increase in limestone contents (relative
to that needed for the original cement) (Fig. 4), and the packing
density decreases (Fig. 5). The low packing density and the
increased number of ‘‘empty’’ spaces within the paste may slow
the setting times despite the larger surface area.
These results suggest that two principal mechanisms—surface
area and packing density—should be considered when discussing
hydration rate behaviors. These two parallel mechanisms entail
opposing influences. Based on the results obtained here, small par-
ticle systems have large surface areas that, although they increase
the hydration rate, they also exhibit lower packing density, which
slows the setting of the paste. When limestone with larger parti-
cles was used, the particles’ surface area was relatively low, leading
to a slow hydration rate, but at the same time to high packing den-
sity (Fig. 5).These results may explain the trends discussed above
and the inconsistency between the hydration rates and surface
areas of the fine particle systems (Figs. 7c and 8).
Combining large and small particles in one blended cement sys-
tem may promote a large surface area and a greater number of
nucleation centers, but at the same time, it will also lead to higher
packing density (Fig. 1) that will speed the hydration process and
decrease the setting time of the paste. Blended cement systems
comprising particle-size combinations are discussed below.
3.3.2. Blended cement systems—combined-particle-size distributions
Blended cement systems in which the original cement was par-
tially replaced with 5% limestone powder containing a combina-
tion of several different particle size distributions were prepared
and investigated. Limestone powders were prepared as follows:
(i) particle sizes of 53 lm (3%) + 3 lm (2%) combined; (ii) particle
sizes of 53 lm (1%) + 3 lm (4%) combined; (iii) 5% single particle
size of 53 lm; and (iv) 5% single particle size of 3 lm. The particle
size combinations clearly had a strong influence on the setting pro-
cess of cement paste (Fig. 10). Combined particle size systems
reduced the time required to reach penetration depths up to final
setting, i.e., increased the hydration rate compared to those of
the original cement paste. Thus, cement blended with the lime-
stone combination of 3% 53-lm + 2% 3-lm particles showed the
shortest time values up to setting among all the tested systems.
It can also be seen that altering the relative contents of the larger
and smaller particles to 1% 53 lm + 4% of 3 lm increased the time
values to reach final setting compared to the combination of 3%
Fig. 10. Penetration depth vs. time behavior of original cement and of cement
pastes blended with single-particle-size or two-particle-sizes with 5% limestone.
31
53 lm + 2% 3 lm. Finally, the longest times up to setting and the
slowest hydration process were obtained for the paste that incor-
porated the large limestone particles (CC53 lm). Note that in order
to reach normal consistency, the amount of water was not the
same for all mixtures, i.e., the water/cement ratio was not the same
for all systems; it was higher for the single-particle-size systems,
0.290 and 0.285 for 3-lm and 53-lm particles, respectively and
0.280 for the combined 3% 53-lm + 2% 3-lm system. For the origi-
nal cement, the water/cement ratio was 0.295. These ratios can
also influence the hydration rates discussed above.
Analysis of the amounts of water required to mix the cement
pastes to normal consistency is presented in Fig. 11a. The figure
shows that significantly less water was required for the cement
system blended with the limestone combination of 3% 53-
lm + 2% 3-lm particles compared with the systems with single-
particle-size distributions (CC53 lm, CC3 lm). The reduced
amount of water needed to reach normal consistency indicates
an increase in the packing density of the blended cement paste
with the combined particle sizes. The calculated packing density
of the different limestone systems with the small and large parti-
cles is presented in Fig. 11b, including that of the original cement.
The figure clearly demonstrates that replacing the original cement
with limestone that is either single-particle-size or combined-par-
ticle-size highly increased the packing density of the paste. Fur-
thermore, replacing the original cement with limestone
containing a combination of several particle size distributions
increased the packing density of the paste compared to the cement
blended with limestone that had only one particle size distribution
(CC53 lm, CC3 lm), mainly for the combined 3% 53-lm + 2%
3 lm-particles. However, increasing the content of the fine lime-
stone powder from 2% to 4% and decreasing the content of the
large-particle limestone from 3% to 1% decreased the packing den-
sity, respectively.
Increases in packing density mean lower paste porosity, which
can lead to significantly decreased setting times of the blended
cement with the combined particle sizes (Fig. 10). Faster time val-
Fig. 11. Properties of original cement and of cement pastes blended with single-
particle-size or two-particle-sizes with 5% limestone: (a) water requirements to
obtain normal consistency related to original cement and (b) calculated packing
density.
32 Y. Knop et al. / Construction and Building Materials 71 (2014) 26–34
ues to reach penetration depths up to final setting were measured
despite the reduced surface area of the combined blended system
(3% 53 lm + 2% 3 lm). Surface area of 1.04% relative to the original
cement was measured for the blended cement with the combined
particle sizes, compared with that of the finest limestone blended
cement system (CC 3 lm) of 1.15%. This trend can be explained by
a combination of both specific surface area and interparticle spac-
ing effects [10,24]. The combined 3% 53-lm + 2% 3-lm particle
system had relatively low surface area compared to the system
with 5% limestone with 3-lm particles, but reduced interparticle
spacing, leading to lower setting times.
The effect of surface area on hydration rate of the blended
cement pastes with 5% limestone was estimated by measuring
the cumulative content of their four main mineral components:
C3S, C2S, C3A, and C4AF using Rietveld quantitative phase analysis
of X-ray diffraction 2.5 h after casting. Calculations of the cumula-
tive content of the blended cement minerals were related to that of
the original cement. The analyzed cumulative contents of the four
mineral components were: 109% and 94%, for the single 53-lm and
single 3-lm limestone blended cements, respectively, related to
the original cement. This indicates greater hydration for the fine
particle blended cement (CC3 lm), i.e., less clinker and faster
hydration rate at age 2.5 h. The effect of the limestone surface area
on the hydration rate was also observed at later ages and with
greater limestone content by analyzing the XRD patterns of
blended cements with CC3-lm and CC25-lm particle sizes and
20% limestone at the age of 1 d (Fig. 12). Fig. 12a presents the full
XRD curves of the two blended cements obtained during testing
with a magnified portion of the XRD pattern. This magnified zone
is highlighted in Fig. 12b, which presents the intensity peaks
related to the two main clinker minerals C3S and C2S of the cement
powder as reported by Yongqi et al. [25]. A clear decrease in the
intensity of this peak can be seen for the finest particle (CC3 lm)
blended cement compared to the blended cement with CC25-lm
limestone. The blended cement with the CC25-lm limestone has
less surface area of 1.371 m2/gr compared with 6.222 m2/gr for
the fine 3CC-lm limestone blended cement (Fig. 3a and Table 2).
Fig. 12. XRD patterns of blended cement with limestone having CC3 lm particles
and CC25 lm, after 1 day of casting: (a) full scale pattern and (b) magnified region
of C3S and C2S peaks.
The reduced intensity of the peak, which indicates the quantity
of the two main clinker minerals C3S and C2S means that the
blended cement with the finer limestone particles (CC3 lm) and
greater surface area contains lower amounts of C3S and C2S, i.e.,
greater hydration and a higher reaction rate of the blended cement
with limestone having more surface area.
Therefore, partial replacement of the original cement with lime-
stone whose surface area was greater than that of the original
cement promoted reaction of a greater volume content of clinker
components with water and their subsequent transformation to
calcium silicate hydrates. This led to an increased volume of the
hydration products and a decrease in setting time (Fig. 7). As
explained in Section 3.3.1, the higher hydration rate was caused
by the increase of the nucleation centers in the blended cement
with the finer limestone filler. In summary, the partial replacement
of the original cement with limestone comprising a combination of
several particle size distributions increases the surface area and the
packing density of the fresh paste—mutual effects that can signifi-
cantly reduce setting times (initial and final).
3.4. Compressive strength
3.4.1. Blended cement systems—one-particle-size distribution
The compressive strengths on days 1 and 28 after casting the
mortar with the cement systems blended with 5% wt. limestone
(particle size 53 lm, 25 lm, or 3 lm) were examined (Fig. 13).
The measured compressive strength of the original cement at 1 d
was 18.3 MPa and at 28 d, it was 65.0 MPa. The coefficient variance
was less than 1% for all tested systems. The ratio between the com-
pressive strength of the blended cement system to the strength of
the original cement system (without added limestone) is pre-
sented. At 1 d, a good correlation is clearly observed between the
blended cement’s compressive strength and the surface area of
the blend. The highest compressive strength was observed for
the blended limestone system with the greatest surface area
(CC3 lm), while the system with the least amount of surface area
had the lowest strength (CC53 lm). In addition, the particle system
with the greater surface area was 4% stronger than the original
cement system, despite the reduction in the active component
(i.e., clinker) in the mortar. Such improved compressive strength
at 1 day of age can be attributed to the increased number of nucle-
ation centers created when limestone is added to cement, as dis-
cussed in Section 3.3.1.
The porosity of the different systems with and without lime-
stone replacement was measured by image analysis using TESCAN
VEGA3 Control software at 1 d. 15 SEM images of each one-
particle-size system: original cement, CC3 lm, CC25 lm, and
Fig. 13. Compressive strengths (days 1 and 28 after casting) of mortars in which the
cement was replaced with 5% limestone powder with mean particle size of either
CC3 lm, CC25 lm, or CC53 lm.
 Y. Knop et al. / Construction and Building Materials 71 (2014) 26–34 33

CC53 lm were analyzed. The estimated porosity values measured

by the image analysis were 7.65%, 11.70%, 13.97%, and 9.16% for
the CC3 lm, CC25 lm, CC53 lm, and the original cement, respec-
tively. Based on these results, a greater volume of pores was dis-
played for blended cement with large-size limestone particles of
25 lm, and this was even more pronounced for the 53-lm parti-
cles compared with the original cement. However, for the fine-
particle blended cement (CC3 lm), the porosity was even lower
than that of the original. This finding correlates strongly with the
compression strength results at 1 day, exhibiting a reduction in
strength for the CC25 lm- and CC53 lm-blended cement systems
compared with that of the original cement. Furthermore, a greater
volume of pores was analyzed in the original cement system com-
pared with the blended limestone cement system with the 3-lm
fine particles, indicating that the fine-particle blended cement sys-
tem had a higher hydration rate, which decreased the porosity by
Fig. 14. Compressive strengths of mortars mixed with 5% limestone powders
1.51% compared to that of the original cement. These findings cor-
comprising either single-particle-size or combined-particle-size distributions using
relate well with the Rietveld quantitative phase analysis results particles measuring 3 lm and/or 53 lm and tested 1 day and 28 days after casting.
(Section 3.3.2, Fig. 12), which revealed greater clinker components
for the blended cement with large-particle limestone (CC53 lm)
compared with the original cement and fewer clinker components
bined blended limestone systems were greater than those of the
for the fine-particle blended cement system at the ages of 2.5 h and
cement blended with single-particle-size limestone.
1 d. Indeed, the reduction in clinker components indicates a higher
The increase observed in 1-day and 28-day post casting com-
degree of hydration, which results in the greater compressive
pressive strengths for cements blended with limestone that had a
strength of the fine-limestone blended system at the age of
combined particle size distribution comprising two particle sizes
1 day. This is in contrast to the increase in clinker components,
can be explained by two mechanisms—the increased degree of
which indicates a lower degree of hydration, resulting in the
hydration and the higher packing density of the powder. As men-
reduced compressive strength of the large-limestone blended sys-
tioned in Section 3.3.2, the effect on the original cement of its par-
tem at the age of 1 day.
tial replacement with limestone depended, in part, on the size of
Compressive strength was also measured 28 days after casting
the limestone particles relative to those of the cement. The incor-
(Fig. 13), but the relationship between the surface area of the
poration of limestone with particles smaller than the cement par-
blended cement powder and compressive strength is not as
ticles increased the hydration degree, while the use of limestone
straightforward as that which was observed 1 day after casting.
whose particles were larger than the cement particles increased
At day 28 after casting, the strongest mixture was the cement
the powder’s packing density. Therefore, partial replacement of
blend with the limestone whose surface area was similar to that
the original cement with limestone that comprises both particle
of the original cement (CC25 lm, Table 2). Both of the other lime-
sizes affects both properties, increasing the degree of hydration
stone particle systems (CC3 lm and CC53 lm) exhibited lower
and the packing density of the mortar at both early and late ages.
strength values that were more pronounced in the mixture with
the fine limestone powder. It is believed that such reductions in
the strength values of the large and fine limestone systems are 4. Conclusions
due to the opposing mechanisms discussed in Section 3.3.1 of
increased packing density for the larger particle systems with This work studied blended cements with three limestone
fewer nucleation centers opposed to the many nucleation centers, powder particle diameters: smaller than, larger than, and simi-
but with lower packing density due to agglomeration of the fine larly sized to the clinker particle. Combined-particle-size vs.
particle system. It can be concluded that the effect of the surface one-particle-size limestone powder distribution systems added
area on the hydration rate had a more significant effect on the to cement mortar were studied and compared in terms of hydra-
properties of the mortar after 1 day, as was also shown by Kumar tion rate, hydration degree, and water demand to achieve normal
et al. [10,11]. On the other hand, decreasing the interparticle spac- consistency. The performances of these systems were also com-
ing and increasing the packing density had a higher effect on the pared with that of the original cement (without added
properties of the mortar after 28 days. Therefore, it is expected that limestone).
greater compressive strength can be achieved after 1 day and also It was found that cement mixtures containing limestone with a
after 28 days by partially replacing the original cement with lime- single-particle-size distribution (smaller than cement particle size)
stone comprising a combination of several particle sizes (larger had an increased hydration rate and hydration degree due to the
than and smaller than the median cement particle size) in the same larger surface area and the increased number of nucleation centers,
powder. characteristic of the small limestone particles. The packing density
under these conditions, however, was lower than that of the origi-
nal cement. Partially replacing the original cement with limestone
3.4.2. Blended cement systems—combined-particle-size distributions whose particles were larger than the original cement particles
Mortar compressive strengths were tested for systems made reduced both the hydration rate and hydration degree due to the
with cement and limestone powder blends, the latter of which con- smaller surface area and the decreased number of nucleation cen-
tained either one or both of two particle sizes (3 lm and 53 lm), ters of the larger limestone particles. Likewise, the packing density
whose relative amounts were varied (Fig. 14). The limestone pow- when using the large particles was greater than that of the original
der mixture that comprised 3% 53-lm and 2% 3-lm particles was cement.
the strongest both at 1 day (10%) and at 28 days (3%) after casting, Blending cements with limestone comprising more than one
compared to the strength of the original cement mortar. Both the particle size was found to significantly increase packing density,
initial and the final strength values (1 day and 28 days) of the com- hydration rate, and hydration degree compared with the original
34 Y. Knop et al. / Construction and Building Materials 71 (2014) 26–34
cement and with cement blended with a limestone powder of a
single particle size. Support for these results was seen in the reduc-
tion of the volume of water required to achieve normal consis-
tency, in the shorter time values for reaching penetration depths
up to final setting, and in the improved compressive strengths at
ages of both 1 day and 28 days after casting.
The results of this work suggest that two main mechanisms—
one related to surface area and the second to powder packing
density—should be taken into consideration when discussing
cements blended with limestone powders and the influences of
those additives on the penetration depths to reach final setting
and on paste compressive strengths at 1 and 28 days after casting.
However, it should be remembered that other mechanisms may
take place when blended cements are considered such as chemi-
cal effects and others. The two parallel mechanisms suggested at
the current work are expressed as follows in blended cement
systems:
 Cement blended with fine limestone particles (i.e., smaller than
those of the cement) produces a paste with a larger surface area
but with lower packing density, as the large surface area leads
to an increased hydration rate, and the lower packing density
increases paste porosity.
 Cement blended with large limestone particles (i.e., larger than
those of the cement) produces a paste with a smaller surface
area, resulting in a slow hydration rate but with higher packing
density.
Cements blended with limestone comprising a combination of
particle sizes can exploit these two mechanisms to create a cement
system both with higher packing density and with a large surface
area. Applied correctly via good design of particle sizes and con-
tents, this approach will enable the development of cement blends
that possess high rates and degrees of hydration and improved
compressive strengths at late ages.
The findings of this study lead to the conclusion that replacing
an active component (the clinker) with an inert additive (lime-
stone) improves cement paste performance by increasing the pack-
ing density of the cement system. This is most pronounced when
the clinker was replaced with limestone powders that comprised
a combination of several different particle sizes.
Acknowledgements
The authors would like to acknowledge the Israel Ministry of
Environmental Protection for their financial support of this
research. Thanks are expressed to Nesher Cement Enterprises
LTD for providing all materials for this study and for their lab
support.
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