Construction and Building Materials 204 (2019) 58–69

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Construction and Building Materials

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

A quantitative study on physical and chemical effects of limestone

powder on properties of cement pastes
Dehui Wang a,b, Caijun Shi c,⇑, Nima Farzadnia c,⇑, Huangfei Jia c, Rong Zeng d, Youwu Wu d, Lilin Lao d
a
State Key Laboratory of Silica Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China
b
College of Civil Engineering, Fuzhou University, Fuzhou 350116, China
c
Key Laboratory for Green & Advanced Civil Engineering Materials and Application Technology of Hunan Province, College of Civil Engineering, Hunan University, Changsha
410082, China
d
China Resources Cement Holdings Limited, Nanning, China

h i g h l i g h t s

The physical and chemical effects of limestone powder (LP) were calculated.

The chemical effect of LP was influenced by its particle size and amount of LP at 3d.

The particle size and amount of LP had little effect on its chemical effect at 180d.

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

Article history: The study aims to quantitatively calculate the physical and chemical effects of limestone powder (LP)
Received 16 October 2018 with four average particle sizes and two amounts in cement pastes by using thermal gravimetric analysis
Received in revised form 11 January 2019 (TGA), X-ray diffraction (XRD), mercury intrusion porosimetry (MIP) techniques. At 3d, as the average
Accepted 25 January 2019
particle size of LP decreased from 32 to 6 lm, the consumed CaCO3 content in LP increased from 0.67%
Available online 2 February 2019
to 1.71%, and the chemically reactive portion of LP increased from 1.15% to 2.95%. However, at 180d,
the consumed CaCO3 content and chemically reactive portion of LP was almost 2.4% and 4.2%, respec-
Keywords:
tively. At 3d, as the LP content increased from 25% to 50%, the consumed CaCO3 content in LP increased
Limestone powder
Cement paste
from 1.71% to 2.02%, and the chemically reactive portion of LP increased from 2.95% to 3.5%. However, at
Physical effect 180d, the differences of consumed CaCO3 content and chemically reactive portion of LP between cement
Chemical effect pastes with different LP content were limited. The physical and chemical effects of limestone powder on
Particle size the compressive strength of cement pastes were calculated. At 180d, as the average particle size of LP
Amount decreased from 32 to 6 lm, the contribution of chemical effect of LP on the compressive strength of
cement pastes increased from 1.01% to 1.08% while the contribution of physical effect decreased from
21.19% to 20.03%.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction tion, such as European standard (EN 197-1) [1], Canadian standard
(CSA A3001-10 [2]), ASTM C595 [3], and Chinese standard (JC/T
Incorporating supplementary cementitious materials (SCMs) 600-2010) [4].
into cement-based composites is a common practice in construc- The action mechanism of limestone powder in cement-based
tion industry owing to their enhancing effect on the concrete prop- materials could be summarized as filler, nucleation, dilution and
erties as well as their low carbon footprint. Among the SCMs, the chemical effects [5]. In 1948, Deniels [6] first reported that the filler
application of limestone powder (LP) is gradually accepted due to effect of LP increased the compressive strength of concrete. When
its wide availability and low cost. In many national standards, it the particle size of LP is smaller than cement, it fills the intraparticle
is permissible to incorporate limestone powder in cement produc- voids between cement particles, improves the particle size distribu-
tion, and increases the packing density of cement-based materials
due to its filler effect [7]. In 1976, Soroka and Setter [8] found the
⇑ Corresponding authors. nucleation effect of LP which promoted the precipitation of C-S-H
E-mail addresses: cshi@hnu.edu.cn (C. Shi), nima.farzadnia@hnu.edu.cn and accelerated the hydration of cement [9]. The nucleation effect
(N. Farzadnia).

https://doi.org/10.1016/j.conbuildmat.2019.01.154
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69 59

of LP was attributed to the similarity between planar configuration limestone powder on the microstructure of cement paste, the
of Ca and O atoms in calcite and CaO layers in C-S-H [10]. Since the chemical reaction between calcium carbonate and aluminum
reactivity of LP is lower than cement particles, when coarser phases was examined by XRD, and the pore structure of cement
limestone powder or a large amount of limestone powder was paste was analyzed by MIP. Moreover, the physical and chemical
incorporated into cement pastes, it mainly showed dilution effect. effects of limestone powder on the compressive strength of cement
The dilution effect of LP decreases the rapid formation of hydration pastes were also discussed.
products and reduces the compressive strength of cement-based
materials [11]. In 1938, Bessey et al. [12] found that CaCO3 reacted
2. Experimental program
with C3A and C4AF to form calcium-carboaluminate. The formation
of calcium-carboaluminate prevented the C3A and C4AF to react
2.1. Raw materials
with ettringite, thus stabilizing the ettringite formation [13].
From the above literatures, the effects of limestone powder on
Portland cement (P I 42.5), limestone powder and tap water
the hydration, microstructure and properties of cement-based
were used in this study. According to Chinese Standards GB175-
materials can be summarized as physical effect and chemical
2007 [18], the compressive strength of Portland cement at 3 and
effect, and the particle size and amount of LP significantly influ-
28d were 26.6 and 57.3 MPa, respectively. The specific surface area
enced its effects on the properties of cement-based materials
of Portland cement was 336 m2/kg. The selected volume weighted
[14].Quantification of physical and chemical effect of limestone
average particle sizes of limestone powder were 32, 20, 8 and
powder will provide a solid and effective theoretical basis for the
6 lm, which respond to limestone powder with a specific surface
use of limestone powder in the engineering practice. Thus far, lim-
area of 500, 650, 800 and 950 m2/kg, respectively. The limestone
ited efforts have been made to investigate the physical effect and
powders with a specific surface area of 500, 650, 800 and
chemical effect of limestone powder quantitatively by changing
950 m2/kg had particle size ranges of 0.578–248.9, 0.486–209.3,
the particle size and amount of the LP. Diederich et al. [15] mea-
0.578–62.23 and 0.486–37 lm, respectively. The specific surface
sured the physical effects of limestone powder on the properties
area of cement and limestone powder were measured by Blaine
of self-compacting concrete (SCC) by determining the maximum
method based on Chinese Standard GB/T 8074-2008 [19]. The cal-
wet packing density of SCC through changing the amount of LP.
cium carbonate content in limestone powder was 93.2% measured
The test results showed that the minimum void ratio of SCC
by thermogravimetric analysis. The main physical properties and
decreased from 0.52 to 0.44 when the amount of limestone powder
chemical compositions of Portland cement and limestone powder
increased from 20% to 26%. On the other hand, thermogravimetric
are shown in Tables 1 and 2, respectively. The mineral composi-
techniques have been used to quantify the chemical effect of lime-
tions of cement were calculated and its results are shown in
stone powder on cement by measuring consumed carbonate con-
Table 3. The particle size distribution of cementitious powders
tent. A study by Arora et al. [16] showed that the particle size of
was measured by the Microtrac S3500 series laser particle size
limestone powder highly influenced its chemical effect, especially
analyzer. The particle size distribution of cement and limestone
at the early age. The normalized consumed carbonate content
powder is illustrated in Fig. 1.
(consumed carbonate content per gram cement) for mixtures con-
taining fine LP were ranged from 14% to 24%, while they ranged
from 7% to 10% for mixtures containing coarse LP at 3d. Moesgaard 2.2. Mixture proportions and curing
et al. [17] reported that the consumed CaCO3 content was 9% when
30% of limestone powder was added to replace cement, but it The water-to-binder ratio of cement pastes was 0.4. The binder
increased to 16% when 10% of calcium aluminosilicate glass and composition was presented in Table 4. Based on the binder compo-
20% of limestone powder was added. sition in Table 4, the cementitious materials and water were mixed
Although the physical and chemical effect of limestone powder together in a drum mixer. The cement pastes were poured into the
on the hydration, microstructure and properties of cement-based steel mold when they were uniform, and then covered with a
materials are comprehensively documented, the quantification of plastic film. After 24 h, the specimens were demolded, moved to
physical and chemical effects of LP based on the particle size and
amount has attracted less attention in the literatures. The overar-
ching aim of this study is to specify the physical and chemical Table 2
effects of LP quantitively based on the particle size and amount Chemical compositions of cement and limestone powder measured by X-ray
of LP using microstructural analysis. In this study, the filler effect fluorescence (XRF) (wt%).

is considered as the only physical effect governing the properties PC LP

of the matrix at later ages of hydration. To reduce the influence SiO2 20.14 0.52
of nucleation effect of limestone powder, the experimental results Al2O3 5.28 0.27
at later age were selected in calculations. Furthermore, to mini- Fe2O3 3.47 0.24
mize the dilution effect of limestone powder, the properties of CaO 63.26 52.66
MgO 2.66 2.66
cement pastes per gram of cement were analyzed instead of per
SO3 2.18 –
gram of binder. TGA was used to measure the consumed carbonate MnO – –
content from the original content as an index to chemical effect of LOI 1.72 43.1
LP. To clarify the influence of physical and chemical effects of

Table 1
Physical properties of cement and limestone powder.

PC LP
2
Surface area (m /kg) 336 500 650 800 950
Specific gravity (kg/m3) 3100 2700 2700 2700 2700
Average particle size (mm) 28.39 32.42 19.92 8.07 5.62
D50(mm) 22.41 18.13 9.10 5.20 4.06
60 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69
Table 3
Calculation results of mineral compositions of cement (wt%).
Mineral composition C3S C2S C3A
Cement 58 14 8 11
standard curing room, and soaked in the Ca(OH)2-saturated water
until the testing age.
2.3. Calculation of the physical and chemical effects of limestone
powder
In this study, the physical and chemical effects of LP were quan-
tified based on their contribution to the density of the specimens.
Since the nucleation effect of LP mainly influences the hydration
degree of cement at early age while it has little effect at later
age, the hydration degree of cement is assumed to be consistent
at later age. Furthermore, to reduce the influence of nucleation
and dilution effects of limestone powder, the experimental results
at later age were considered in the calculations, and the properties
of cement pastes per gram of cement were analyzed instead of per
gram of binder. Thus, the density of cement pastes could be
expressed by the following equation:
Density of paste ðPÞ ¼ Contribution of cement hydration
þ Contribution of physical effect
of limestone powder
þ Contribution of chemical effect of
limestone powder
where, P: density of paste;
Contribution of physical effect of limestone powder: The vol-
ume of limestone powder that only displays physical effect is
divided by the total volume of paste;
Contribution of chemical effect of limestone powder: The vol-
ume of limestone powder that only displays chemical effect is
divided by the total volume of paste, and it could be expressed
as the volume before the chemical reaction plus the volume change
before and after the chemical reaction.
Contribution of cement hydration ¼ Pc  ac
where, Pc: the density of pure cement paste;
ac: the mass proportion of cement in cementitious materials.
Contribution of physical effect of limestone powder
mb  ðaLP  bÞ=qLP
¼ ð3Þ
mb  ða þ 1Þ=q
where, mb: the mass of binder;
aLP: the mass proportion of limestone powder in cementitious
materials;
b: the mass proportion of chemical reaction of limestone
powder;
qLP: the apparent density of limestone powder;
a: the water to binder ratio of paste = 0.4;
q: the density of paste.
Contribution of chemical effect of limestone powder
mb  b=qLP þ mb  b  Dv =MLP
¼ ð4Þ
mb  ða þ 1Þ=q
where, Dv: the volume change before and after the chemical reac-
tion of limestone powder;
MLP: the molar mass of limestone powder.
Based on Eqs. (1)–(4), the density of paste could be expressed by
Eq. (5):
aLP bÞ=qLP mb b=qLP þmb bDv =MLP
P ¼ Pc  ac þ mbmððaþ1Þ= q þ mb ðaþ1Þ=q
b
aLP =qLP bDv =M LP
¼ Pc  ac þ ðaþ1Þ= q þ ðaþ1Þ=q
ð5Þ
C4AF
aLP q bqDv
¼ Pc  ac þ ðaþ1Þ qLP þ ðaþ1ÞMLP
The chemically reactive portion of limestone powder per gram
of cement could be calculated by Eq. (6):
b=qLP þbDv =MLP
ðaþ1Þ=q
Y¼ ð6Þ
ðP  Pc  ac Þ  mc
where, Y is the volume of chemical reaction of limestone powder
per gram of cement divided by the total volume of limestone
powder;
mc: the mass of cement in cement pastes.
The volume change before and after the chemical reaction of
limestone powder could be obtained from Eqs. (7.a) and (7.b) [13]:
 
C 3 A þ 0:5C C þ0:5CH þ 11:5H ! C 4 AC 0:5 H12
89 cm3 =mol þ 0:5  37 cm3 =mol þ 0:5  33 cm3 =mol ð7:aÞ
! 285 cm =mol; DV ¼ 130 Vol%
3
 
C 3 A þ C C þ11H ! C 4 A C H11
89 cm3 =mol þ 37 cm3 =mol ! 262 cm3 =mol; DV ¼ 108 Vol%
ð7:bÞ
In Eq. (6), qLP, Dv, MLP, a, q ac and mc are known or easy to be
measured. By measuring the residual LP content at different age
through thermogravimetric analysis, the mass proportion of chem-
ical reaction of limestone powder (b) could be calculated according
ð1Þ to the initial LP content. By measuring the porosity of cement
pastes through mercury intrusion porosimetry, the density of
cement pastes (P and Pc) could be calculated. Combining the Eqs.
(6) and (7) with the experimental results of thermogravimetric
analysis and mercury intrusion porosimetry, the chemically reac-
tive portion of limestone powder in cement pastes with different
mixture proportions could be calculated, and the physical effect
of LP could be obtained by subtraction of chemically consumed
carbonate from the total original carbonate content in the LP.
2.4. Experimental methods
ð2Þ
To obtain the required parameters of the calculation, the below
examinations were conducted. The hydration heat of cement paste
was measured to identify the extent of the nucleation effect of LP
in the hydration process. The thermogravimetric analysis was
applied to measure the calcium carbonate content present in the
matrix at different ages of hydration. According to the initial cal-
cium carbonate content from the mixture proportions, the con-
sumed calcium carbonate content was calculated, and physical
effect of LP could be obtained by subtraction of chemically con-
sumed carbonate from the total original carbonate content. XRD
examination was conducted to trace the products of calcium car-
bonate reactions targeting the formation of calcium-
carboaluminate to be used in Eq. (7). To measure the density in
the Eq. (6), the MIP was employed. The compressive strength of
cement paste was obtained to illustrate the physical and chemical
effects of LP at macro levels. To prevent the carbonation of hydra-
tion products, the operation of sampling, milling and drying, etc.
were handled in anhydrous alcohol solution or in the environment
where humidity was greater than 95%.
2.4.1. Heat of hydration
The heat evolution rate and heat of hydration of cement pastes
containing limestone powder were determined by a TAMAIR
isothermal calorimeter. The temperature of the equipment was
 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69
100
80
LP-20<mu>m
Cumulative volume (%)
60
LP-8<mu>m
40
LP-6<mu>m
20
0 0
1 10
Particle size (<mu>m)
Fig. 1. Particle size distribution of cement and limestone powder.
Table 4
Binder composition of pastes.
No PC (%) LP (%)
1 100 0 /
2 75 25
3 75 25
4 75 25
5 75 25
6 50 50
7 50 50
8 50 50
9 50 50
controlled at (20 ± 0.02) °C. Approximately 4 g samples were filled
into a glass bottle, and they were placed into the TAMAIR isother-
mal calorimeter. The experiment lasted for 72 h, and the test data
was stored.
2.4.2. Thermogravimetric analysis
Until the test age, a block sample at the central part of speci-
mens was selected and put into the absolute alcohol solution to
stop the hydration reaction. Then, the sample was dried in a vac-
uum oven at 60 °C for 24 h until its weight was constant. The sam-
ple was ground into fine powder and passed through a sieve of
45 lm. These powders were placed in a furnace of thermal detec-
tor, and the instrument was controlled by a computer to raise the
temperature from 20 °C to 1000 °C at heating rate of 10 °C/min.
The thermogravimetric and differential thermal scanning curves
were recorded.
2.4.3. X-ray diffraction (XRD)
Until test age, a block sample at the central part of specimens
was selected and put into the absolute alcohol solution to stop
the hydration reaction. Then, the sample was taken from the abso-
lute alcohol solution, ground into fine powder and passed through
a 300 mm mesh sieve. The fine powder was dried in a vacuum oven
at 60 °C for 48 h until its weight was constant. The phase analysis
was analyzed by XRD using a Philips X-ray diffractometer. The
samples were scanned between 8° and 13°.
2.4.4. Mercury intrusion porosimetry (MIP)
Until test age, a block sample at the central part of specimens
was selected and put into the absolute alcohol solution to stop
the hydration reaction. Then, the sample was taken from the abso-
61
100 lute alcohol solution and dried in a vacuum oven at 60 °C for 24 h
until its weight was constant. The porosity and pore size distribu-
tion of the samples were measured by MIP using a PoreMaster-60
80 automatic mercury porosimeter with a maximum pressure of
414 MPa. The contact angle between mercury and the pore wall
was 140°, and the surface tension of mercury was 480 erg/cm2.
60 The test age for pore structure of samples were 28 and 180d.
PC 40 2.4.5. Compressive strength
The compressive strengths of specimens at 3, 7, 14, 28, 90 and
180d were measured according to Chinese Standards GB/T
LP-32<mu>m
20 17671-1999 [20]. The specimens size was 40 mm  40 mm 
40 mm, and the loading rate of specimens was (2.4 ± 0.2) kN/s.
The compressive strength test results were the average of three
specimens tested at the same age.
100 1000
3. Results and discussion
3.1. Determination of the nucleation effect of limestone powder
The nucleation effect of limestone powder influences the heat
evolution, hydration products, microstructure and properties of
Average particle size (lm)
cement pastes at early ages. Therefore, before analyzing the phys-
ical and chemical effects of limestone powder, it is necessary to
32
clarify the extent to which the nucleation effect of limestone pow-
20
8 der influences the early properties of cement pastes.
6 Figs. 2 and 3 show the effects of particle size and amount of
32 limestone powder on the normalized heat evolution rate and nor-
20 malized heat of hydration of cement pastes, respectively. From
8
6
Figs. 2(a) and 3(a), it can be seen that with the decrease of particle
size or the increase of amount of limestone powder, the main
hydration peak accelerated, the C3S hydration peak increased,
and the slope of curve for the accelerated period steepened. Figs. 2
(b) and 3(b) illustrate that the incorporation of limestone powder
also increased the normalized hydration heat of cement pastes.
The test results demonstrated that at early age, the particle size
and amount of limestone powder affected the hydration kinetics
through its nucleation effect, and it was enhanced as the particle
size decreased or the amount of limestone powder increased. Since
the planar configuration of Ca and O atoms in calcite is similar with
the CaO layers in C-S-H, C-S-H can precipitate on the surface of
limestone powder [10]. The precipitation of C-S-H on the surface
of calcite promotes the further hydration of cement. As a result,
the incorporation of fine limestone powder accelerated the hydra-
tion reaction of C3S and improved the hydration degree of cement
[11]. The early age hydration of mixtures containing fine limestone
powder with median particle size of 0.7 and 3 lm was accelerated,
while the early age hydration of mixture containing 15 lm was
similar with control group [21]. With the increase of limestone
powder amount, more nucleation sites would be available, and
more hydration products could be precipitated [22].
From the above test results, it can be stated that the nucleation
effect of limestone powder on the hydration of cement pastes at
the early age was obvious. The hydration degree of cement pastes
containing limestone powder at the early age was higher than
cement paste without limestone powder. However, the nucleation
effect of limestone powder on the properties of cement pastes at
the later age was little. Thus, the hydration degree of cement at
later age was assumed to be the same in this study, and the chem-
ical effect of limestone powder on the properties of cement pastes
at the early age was inevitably underestimated. To reduce the
nucleation effect of limestone powder, the physical and chemical
effects of limestone powder was calculated based on the properties
of cement pastes at later age.
62 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69

16
Heat evolution rate (kJ/(kgcement*h))

300
14 LP-8<mu>m

Heat of hydration (kJ/(kgcement))

LP-6<mu>m
LP-20<mu>m 250
12
LP-32<mu>m
10 200
LP-20<mu>m
LP-8<mu>m
8
150
6 LP-6<mu>m
Reference 100
4
LP-32<mu>m
2 50
Reference
0 0
0 12 24 36 48 60 72 0 12 24 36 48 60 72
Time (h) Time (h)

(a) (b)
Fig. 2. Effect of average particle size of LP (PC: LP = 75:25) on (a) normalized heat evolution rate; (b) normalized heat of hydration.

16
Heat evolution rate (kJ/(kgcement·h))

14 300
Heat of hydration (kJ/(kgcement))

PC:LP=50:50(%)
12 250

10
200
8 PC:LP=75:25(%)
150
PC:LP=50:50(%)
6
100
4 PC:LP=100:0(%) PC:LP=75:25(%)
50
2
PC:LP=100:0(%)
0 0
0 12 24 36 48 60 72 0 12 24 36 48 60 72
Time (h) Time (h)
(a) (b)
Fig. 3. Effect of amount of LP (average particle size: 6 lm) on (a) normalized heat evolution rate; (b) normalized heat of hydration.

3.2. The chemical reaction between limestone powder and aluminum 3d, and the formation of mono-carbonate was enhanced with the
phases decrease of particle size or the increase of amount of LP at 28d.
The test results are consistent with the trend of thermogravimetric
Fig. 4 shows the thermogravimetric analyses of cement paste analysis. According to the XRD test results, the formation of car-
containing 6 lm limestone powder at a replacement level of 25% boaluminates could be confirmed, and the chemical reaction
at different ages. To facilitate the observation, the results of 3, 28 between limestone powder and aluminum phases as shown in
and 90d were selected to illustrate. As can be seen, a peak at Eq. (7) was verified. With the increase of amount of limestone
180 °C was formed and it increased with age, which might be powder, the peak of hemi-carbonate and mono-carbonate
attributed to the formation of carboaluminate [23,24]. It was increased [23,25].
reported that the aluminate phases in cement reacted with CaCO3
to form mono- and hemi-carbonate when LP was incorporated into 3.3. Measuring the chemical reaction rate of limestone powder
cement-based materials [13]. To confirm whether the new hydra-
tion product corresponding to the 180 °C decomposition peak in The calcium carbonate content was measured by thermogravi-
thermogravimetric analysis curve is carboaluminate, the cement metric analysis with respect to the mass loss associated to the peak
pastes were analyzed using XRD. The XRD diffraction peaks associ- at about 750 °C. The consumed calcium carbonate content was cal-
ated to mono- or/and hemi-carbonate are detected at 11.7° and culated by subtracting the residual calcium carbonate content from
10.8° 2h, respectively [25]. the initial content. The consumed CaCO3 can could be expressed by
Figs. 5 and 6 show the XRD patterns of pastes with LP of differ- the following equation:
ent average particle size and amount, respectively. It can be
ab
observed that the formation of hemi-carbonate increased with Consumed CaCO3 contentðcÞ ¼  100% ð8Þ
a
the decrease of particle size or the increase of amount of LP at
 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69 63

0 200 400 600 800 1000

0.0 0.0 0 200 400 600 800 1000
100 100
-0.2 -0.2 3d
28d
-0.4 -0.4 95 90d 95
DTG (wt. %/oC)

-0.6 -0.6
90 90

TG (wt.%)
-0.8 -0.8
-1.0 -1.0 85 85
-1.2 -1.2
-1.4 -1.4 80 80

-1.6 3d -1.6 75 75
-1.8 28d -1.8
90d 70 70
-2.0 -2.0
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature (oC) Temperature (oC)
(a) (b)
Fig. 4. Thermal gravimetric analyses of pastes (PC: LP = 75:25, average particle size of LP: 6 lm): (a) DTA curves; (b) TGA curves.

Fig. 5. Effect of average particle size of LP on the hydration products of cement pastes (PC: LP = 75:25). The main peaks of ettringite (E), hemicarbonate (Hc), monocarbonate
(Mc) and ferrite phase (F) were observed.

where, a (%): initial CaCO3 content;
b (%): residual CaCO3 content;
Consumed CaCO3 content: the proportion of CaCO3 content
reacted per gram of cement.
3.3.1. Particle size of limestone powder
Fig. 7 shows the effect of particle size of LP on the consumed
CaCO3 content in the cement pastes (PC: LP = 75:25) during 180d
of hydration. As seen, the particle size affected the consumed
CaCO3 content of cement pastes significantly at early ages, but its
effect reduced as the age prolonged to 180d. The incorporation of
finer limestone powder increased the CaCO3 consumption at 3d.
The consumed CaCO3 content of cement pastes containing 25% of
limestone powder with an average particle size of 32, 20, 8 and
6 lm at 3d were 0.67%, 1.07%, 1.54% and 1.71%, respectively. How-
ever, the consumed CaCO3 contents of cement pastes were almost
2.4% at 180d. With the decrease of particle size of limestone pow-
der, the dissolution rate and reactivity of CaCO3 in limestone pow-
der increased. Thus, with the decrease of particle size of limestone
powder, the consumed CaCO3 content of cement pastes at early age
increased. At later ages, the amount of dissolved CaCO3 was suffi-
cient for its reaction, and the consumed CaCO3 content of cement
pastes was similar regardless of the particle size of limestone pow-
der. It was also reported [16] that more than 10% of CaCO3 was
consumed in mixtures containing fine limestone powder while
around 5% of CaCO3 was consumed in mixtures containing coarse
limestone powder at 3d. However, the consumed CaCO3 content
of cement pastes at 28d was similar. From the test results, it can
be deduced that the physical effect of limestone powder, as an
inverse proportion to its chemical effect, decreased as the hydra-
tion age prolonged and the influence of the particle size remained
constant at later age.
3.3.2. Amount of limestone powder
Fig. 8 shows the effect of amount of limestone powder (average
particle size: 6 lm) on the consumed CaCO3 content of cement
pastes. As seen, higher amount of limestone powder increased
the consumed CaCO3 content of cement pastes at all ages. How-
64 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69

Fig. 6. Effect of amount of LP (average particle size: 6 lm) on the hydration products of cement pastes. The main peaks of ettringite (E), hemicarbonate (Hc), monocarbonate
(Mc) and ferrite phase (F) were observed.

2.6
2.4
Consumed CaCO3 content (%/gcement)
Consumed CaCO3 content (%/gcement)

2.2
2.0 2.4

1.8
1.6 2.2

1.4
1.2 2.0
1.0 LP-32<mu>m
LP-20<mu>m
0.8 1.8
LP-8<mu>m
PC:LP=75:25
0.6 LP-6<mu>m
PC:LP=50:50
0 20 40 60 80 100 120 140 160 180
0 20 40 60 80 100
Time (d)
Time (d)
Fig. 7. Effect of average particle size of LP on the consumed CaCO3 content of
cement pastes (PC: LP = 75:25). Fig. 8. Effect of amount of LP (average particle size: 6 lm) on the consumed CaCO3
content of cement pastes.

3.4. Measuring the density of cement pastes

ever, the effect of amount of limestone powder on the consumed
CaCO3 content of cement pastes was greater at early ages than that
Based on Eq. (6), the density of cement pastes and control group
at later days. The consumption of CaCO3 was 2.02% in cement paste
are required to calculate the chemically reactive portion of lime-
containing 50% LP at 3d, and it was 1.71% in cement paste contain-
stone powder per gram of cement. Accordingly, the density of
ing 25% LP. Zajac et al. [25] also reported that the content of car-
cement pastes and control group was measured by mercury intru-
boaluminates of cement-based materials containing 3% and 9%
sion porosimetry.
limestone powder was higher than that of cement-based materials
containing 1% limestone powder. The increase of amount of lime-
stone powder triggered the formation of carboaluminate and the 3.4.1. Particle size of limestone powder
consumed CaCO3 content of cement pastes increased. The results Fig. 9 shows the pore size distribution and cumulative porosity
from the LP amount was also indicative of the decreased effect of of cement pastes (PC: LP = 75:25) with different particle sizes of LP.
physical effect as the age increased. To facilitate the observation, the results of three groups were
 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69 65

selected to illustrate. It can be observed that the particle size of
limestone powder significantly influenced the most probable pore
diameter and porosity of cement pastes. The most probable pore
diameter of cement pastes at 28d incorporating LP with an average
particle size of 32, 20, 8 and 6 lm were 56.9, 53.2, 52.6 and
48.9 nm, respectively. At the same time, the porosity of the speci-
mens was 31.37%, 30.09%, 29.92% and 29.30%, respectively. Previ-
ously, it was reported that the CaCO3 in limestone powder reacts
with aluminate phases in cement and supplementary cementitious
materials to form hemi- and mono-carbonate [13] and prevents
the decomposition of ettringite [26]. The formation of mono- and
hemi-carbonate increases the solid phase volume of cement-
based materials by 108–130% [13]. At 25 °C, the molar volume of
ettringite and monosulphate is 707 and 309 cm3/mol, respectively.
Ettringite is more voluminous than monosulphate [27]. The pre-
vention of the decomposition of ettringite also increases the solid
phase volume of cement-based materials. At 180d, the porosity
of cement pastes decreased to 26.17%, 25.69%, 26.85% and
26.57%, respectively owing to the ongoing hydration. The results
showed that the effect of particle size of LP on the porosity of
cement pastes decreased as the age prolonged. As discussed in Sec-
tion 3.3, the chemical effect of limestone powder was enhanced
with the decease of particle size of limestone powder at 28d, while
the influence of the particle size on chemical reactions was similar
at 180d. Therefore, the changes in the most probable pore diameter
and porosity of cement pastes at later age should be mainly influ-
enced by the physical effects of limestone powder. From Fig. 1, it
can be seen that the particle size distributions of limestone powder
with an average particle size of 32 and 20 lm were within a wide
range. Therefore, the incorporation of limestone powder might
improve the packing density of cement pastes. As seen, the most
probable pore diameter and porosity of cement pastes were mini-
mum at 180d when limestone powder with an average particle
size of 20 lm was applied.
3.4.2. Amount of limestone powder
Fig. 10 shows the effect of amount of LP (average particle size:
6 lm) on the pore size distribution and cumulative porosity of
cement pastes. The amount of limestone powder significantly
influenced the most probable pore diameter and porosity of
cement pastes. At 28d, the most probable pore diameter of cement
pastes containing 0%, 25% and 50% of limestone powder with an
average particle size of 6 lm were 40.6, 48.9 and 77.2 nm, respec-
tively, and the porosity were 27.14%, 29.30% and 35.52%, respec-
tively. Unlike the particle size effect, the influence of amount on
the pore structure was remarkable at later ages. At 180d, the

0.01 0.1 1 10 100

0.01 0.1 1 10 100 35 35
0.35 0.35
30 30
0.30 0.30
25 Reference 25
dv/dlog(d) (cc/g)

0.25 0.25
Porosity (%)

LP-32<mu>m
20 20
0.20 0.20
LP-6<mu>m

0.15 0.15 15 15
LP-6<mu>m

0.10 0.10 10 10
LP-32<mu>m

0.05 Reference 0.05 5 5

0.00 0.00 0 0
0.01 0.1 1 10 100 0.01 0.1 1 10 100
Pore diameter (<mu>m) Pore diameter (<mu>m)
(a) (b)

0.01 0.1 1 10 100 0.01 0.1 1 10 100

0.35 0.35 35 35

0.30 0.30 30 30

0.25 0.25 25 25
dv/dlog(d) (cc/g)

Porosity (%)

0.20 0.20 20 20
LP-6<mu>m
0.15 0.15 15 15
LP-32<mu>m
0.10 0.10 10 10
LP-6<mu>m Reference

0.05 LP-32<mu>m 0.05 5 5

Reference
0 0
0.00 0.00
0.01 0.1 1 10 100
0.01 0.1 1 10 100
Pore diameter (<mu>m) Pore diameter (<mu>m)
(c) (d)
Fig. 9. Effect of average particle size of LP on the pore size distribution and cumulative porosity of cement pastes (PC: LP = 75:25): (a) pore size distribution at 28d; (b)
cumulative porosity at 28d; (c) pore size distribution at 180d; (d) cumulative porosity at 180d.
66 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69

porosity was 23.00%, 26.57% and 33.77%, respectively when 0%,
25% and 50% of LP were applied. It was documented [28] that
incorporation of greater fraction of limestone powder as a substitu-
tion to cement decreased the content of cement clinker and the
hydration products. The incorporation of limestone powder might
show its dilution effect when the amount of limestone powder
exceeds a certain amount. It was also reported [29] that when
enough coarse limestone powder was incorporated into cement-
based materials, the porosities of cement-based materials were
higher than that of control group without limestone powder. The
amount of limestone powder was 25% and 50% in this study, and
it is high enough to show its dilution effect. Thus, the incorporation
of limestone powder increased the most probable pore diameter
and porosity of cement pastes at all ages.
3.5. Quantification of the physical and chemical effects of limestone
powder
3.5.1. Particle size of limestone powder
Fig. 11 shows the effect of particle size of LP on its chemically
reactive portion in cement pastes (PC: LP = 75:25). The effect of
particle size of limestone powder on its chemically reactive portion
in cement pastes was obvious at 3d, but the chemical effect was
similar as the age prolonged to at 180d, which was consistent with
the results in Section 3.3. With the decrease of particle size of lime-
stone powder, the chemically reactive portion of limestone powder
in cement pastes at each age increased. The chemically reactive
portion of limestone powder in cement pastes containing 25% of
limestone powder with an average particle size of 32, 20, 8 and
6 lm at 3d were 1.15%, 1.85%, 2.67% and 2.95%, respectively. At
180d, it increased to 3.97%, 4.13%, 4.13% and 4.20%, respectively.
As mentioned earlier, the physical effect of limestone powder on
cement paste was inversely proportional to its chemical effect. As
discussed in Section 3.3, with the decrease of particle size of lime-
stone powder, the dissolution rate and reactivity of CaCO3 in lime-
stone powder increases. Thus, with the decrease of particle size of
limestone powder, the chemically reactive portion of limestone
powder in cement pastes at early age increased. At later age, the
amount of dissolved CaCO3 was sufficient for its reaction, and the
chemically reactive portion of limestone powder in cement pastes
was similar regardless of the particle size of limestone powder.
3.5.2. Amount of limestone powder
Fig. 12 shows the effect of amount of limestone powder (aver-
age particle size: 6 lm) on its chemically reactive portion in
cement pastes. As seen, the effect of amount of limestone powder

0.40 35

0.35
30
0.30
25
dv/dlog(d) (cc/g)

0.25
Porosity (%)

PC:LP=75:25 (%)
20
0.20
PC:LP=50:50 (%)
15
0.15 PC:LP=50:50 (%)

PC:LP=75:25 (%) 10 PC:LP=100:0 (%)

0.10

0.05 PC:LP=100:0 (%) 5

0.00 0
0.01 0.1 1 10 100 0.01 0.1 1 10 100

Pore diameter (<mu>m) Pore diameter (<mu>m)

(a) (b)

0.40 35

0.35 30

0.30
25
dv/dlog(d) (cc/g)

Porosity (%)

0.25
20
0.20
PC:LP=50:50 (%) 15 PC:LP=50:50 (%)
0.15
10 PC:LP=75:25 (%)
0.10 PC:LP=75:25 (%)
5 PC:LP=100:0 (%)
0.05 PC:LP=100:0 (%)

0.00 0
0.01 0.1 1 10 100 0.01 0.1 1 10 100
Pore diameter (<mu>m) Pore diameter (<mu>m)

(c) (d)
Fig. 10. Effect of amount of LP (average particle size: 6 lm) on the pore size distribution and cumulative porosity of cement pastes: (a) pore size distribution at 28d; (b)
cumulative porosity at 28d; (c) pore size distribution at 180d; (d) cumulative porosity at 180d.
 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69 67

0 5 10 15 20 25 30 35 40 25 50
5.0 5.0 4.5 4.5
3d
Chemically reactive portion (%/gcement)

Chemically reactive portion (%/gcement)

7d
14d
4.0 28d 4.0
90d 4.0 4.0
180d
3.0 3.0

3.5 3.5
2.0 2.0

3d
1.0 1.0 7d
3.0 14d 3.0
28d
0.0 0.0 90d
0 5 10 15 20 25 30 35 40 180d
Particle size (<mu>m) 2.5 2.5
25 50
Fig. 11. Effect of average particle size of LP on its chemically reactive portion in
Amount of LP (%)
cement pastes (PC: LP = 75:25).

Fig. 12. Effect of amount of LP (average particle size: 6 lm) on its chemically
on its chemically reactive portion in cement pastes at the early age reactive portion in cement pastes.
was greater than that at later days. With the increase of amount of
LP, its chemically reactive portion in cement pastes at each age
increased. The chemically reactive portion of limestone powder 5 10 15 20 25 30 35 40
in cement pastes containing 25% of limestone powder with an 3d
average particle size of 6 lm at 3, 7, 14, 28, 90 and 180d were 60 7d 60
2.95%, 3.21%, 3.58%, 3.76%, 3.93% and 4.20%, respectively. The 14d
Compressive strength (MPa)

chemically reactive portion of limestone powder in cement pastes 28d

containing 50% limestone powder with an average particle size of 90d
50 180d 50
6 lm at 3, 7, 14, 28, 90 and 180d were 3.50%, 3.63%, 3.82%,
4.02%, 4.17% and 4.29%, respectively. It was reported [23] that
the content of carboaluminate of cement-based materials contain- 40 40
ing 3% and 9% limestone powder was higher than that of cement-
based materials containing 1% limestone powder. Thus, with the
increase of amount of limestone powder, the formation of carboa-
30 30
luminate increased and its chemically reactive portion in cement
pastes increased.
20 20
3.6. Compressive strength 5 10 15 20 25 30 35 40
Particle size (<mu>m)
3.6.1. Particle size of limestone powder
Fig. 13 shows the effect of particle size of limestone powder on Fig. 13. Effect of particle size of LP on the compressive strength of cement pastes
compressive strength of cement pastes (PC: LP = 75:25). As seen, (PC: LP = 75:25).

the particle size of limestone powder significantly influenced the

compressive strength of cement pastes, especially at early ages.
As discussed in Sections 3.3 and 3.5, the chemical effect of lime-
stone powder was enhanced with the decease of particle size of
limestone powder at 3d, whereas, the effect of particle size on its
chemical effect was similar at 180d. Thus, at 3d, the compressive
strength of cement paste containing limestone powder with an
average particle size of 6 lm was the highest. Since the particle
size distribution of limestone powder with an average particle size
of 20 lm was within a wide range, the incorporation of limestone
powder might improve the packing density of cement pastes. As a
result, at 180d, the compressive strength of cement pastes contain-
ing limestone powder with an average particle size of 20 lm was
the highest. It has reported [30] that incorporating ultra-fine lime-
stone powder improved the compressive strength of concrete due
to filler effect. The compressive strength of concrete increased with
the decrease of particle size of limestone powder [31]. However,
the dilution effect of limestone powder masked other effect, and
reduced the compressive strength of concrete when limestone
powder surpassed a certain amount [32]. The contribution of phys-
ical and chemical effects of LP could be calculated according to Eqs.
(3) and (4). The contribution of limestone powder on the compres-
sive strength was related to its contribution on density of cement
pastes. Table 5 shows the contribution of the physical and chemical
effects of LP on the compressive strength of cement pastes.
3.6.2. Amount of limestone powder
Fig. 14 shows the effect of amount of limestone powder (aver-
age particle size: 6 lm) on the compressive strength of cement
pastes. As seen, the amount of limestone powder significantly
influenced the compressive strength of cement pastes. With the
increase of amount of limestone powder, the compressive strength
of cement pastes decreased, which was consistent with the exper-
imental results in Section 3.4. As discussed in Section 3.4, the
incorporation of a large amount of limestone powder mainly trig-
gers its dilution effect. Thus, the incorporation of limestone pow-
der decreased the compressive strength of cement pastes,
especially at 180d. The dilution effect of limestone powder
decreased the rapid formation of hydration products, and reduced
the compressive strength of concrete [11]. It has confirmed that
incorporating 5% [32], 25% [33] and 35% [34] limestone powder
into concrete decreased the compressive strength of concrete,
especially at later age. Table 6 shows the contribution of the phys-
68 D. Wang et al. / Construction and Building Materials 204 (2019) 58–69

Table 5
Contribution of physical and chemical effects of LP with different particle size on the compressive strength of cement pastes.

Average particle size Contribution of physical effect at Contribution of chemical effect at Contribution of physical effect at Contribution of chemical effect at
(lm) 28d (%) 28d (%) 180d (%) 180d (%)
32 21.71 0.32 21.19 1.01
20 21.21 0.75 21.07 1.02
8 21.09 0.85 20.93 1.05
6 20.05 1 20.03 1.08

the amount of LP increased from 25% to 50%, the consumed CaCO3

0 25 50
content at 3d increased from 1.71% to 2.02% while the difference of
3d consumed CaCO3 content at 180d was limited.
7d The effects of particle size of limestone powder on the pore size
80 distribution and cumulative porosity of cement pastes at different
14d 80
Compressive strength (MPa)

ages were different. At 28d, the most probable pore diameter

28d decreased from 56.9 to 48.9 nm and porosity of cement pastes
90d decreased from 31.37% to 29.30% as the average particle size of
60 180d 60 limestone powder decreased from 32 to 6 lm. The most probable
pore diameter increased from 40.6 to 77.2 nm, and the porosity
increased from 27.14% to 35.52% as the amount of LP increased
from 0% to 50%. At 180d, the most probable pore diameter and
40 40
porosity of cement pastes containing limestone powder with an
average particle size of 20 lm were the lowest.
As the average particle size of LP decreased from 32 to 6 lm, the
20 20 chemically reactive portion at 3d increased from 1.15% to 2.95%
while the chemically reactive portion at 180d was about 4.2%. As
the amount of LP increased from 25% to 50%, the chemically reac-
0 25 50 tive portion at 3d increased from 2.95% to 3.5% while the chemi-
Amount of LP (%) cally reactive portion of LP at 180d was similar.
The physical and chemical effects of limestone powder on the
Fig. 14. Effect of amount of LP (average particle size: 6 lm) on the compressive
strength of cement pastes. compressive strength of cement pastes were calculated. As the
average particle size of LP decreased from 32 to 6 lm, the contribu-
tion of physical effect of LP on the compressive strength of cement
Table 6
pastes decreased from 21.71% to 20.05% while the contribution of
Contribution of physical and chemical effects of LP with different amount on the
compressive strength of cement pastes. chemical effect increased from 0.32% to 1% at 28d, and the contri-
bution of physical effect decreased from 21.19% to 20.03% while
Amount Contribution of Contribution of Contribution of Contribution of
the contribution of chemical effect increased from 1.01% to 1.08%
(%) physical effect chemical effect physical effect chemical effect
at 28d (%) at 28d (%) at 180d (%) at 180d (%) at 180d. As the amount of LP increased from 25% to 50%, the con-
tribution of physical effect of LP on the compressive strength of
25 20.05 1 20.03 1.08
50 42.02 2.66 41.97 2.84
cement pastes increased from 20.05% to 42.02% while the contribu-
tion of chemical effect increased from 1% to 2.66% at 28d, and the
contribution of physical effect increased from 20.03% to 41.97%
ical and chemical effects of LP on the compressive strength of while the contribution of chemical effect increased from 1.08% to
cement pastes. 2.84% at 180d.
The test results of compressive strength of cement pastes were
consistent with the pore structure of cement pastes, and the phys-
ical and chemical effect of LP on the compressive strength of Conflict of interest
cement pastes were calculated, which could provide a theoretical
basis for the application of limestone powder in practical The authors declare that there is no conflict of interest.
engineering.
Acknowledgement
4. Conclusions
Financial supports from National Science Foundation of China
under contract Nos. 51608187 is greatly appreciated. The project
In this study, the quantitative study on the physical and chem-
was also supported by China Postdoctoral Science Foundation
ical effects of limestone powder in cement pastes were investi-
(No. 2017M612551) and State Key Laboratory of Silicate Materials
gated. The following conclusions can be drawn:
for Architectures (Wuhan University of Technology) (No.
With the decrease of particle size or the increase of amount of
SYSJJ2017-07).
limestone powder, the nucleation effect of limestone powder was
obvious. To reduce the nucleation effect on the calculation of phys-
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