Construction and Building Materials 181 (2018) 659–672

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Construction and Building Materials

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Review

A review on use of limestone powder in cement-based materials:

Mechanism, hydration and microstructures
Dehui Wang a, Caijun Shi b,⇑, Nima Farzadnia b, Zhenguo Shi c, Huangfei Jia b, Zhihua Ou d
a
College of Civil Engineering, Fuzhou University, Fuzhou 350116, China
b
College of Civil Engineering, Hunan University, Changsha 410082, China
c
Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Aarhus C 8000, Denmark
d
School of Civil Engineering, Hunan University of Technology, Zhuzhou 412007, China

h i g h l i g h t s

The action mechanism of limestone powder includes four effects.

The physical effect of limestone powder depends on its particle size and amount.

The chemical effect of limestone powder relies on the alumina content.

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

Article history: Limestone powder (LS) has been widely used in cement-based materials; and reportedly, can influence
Received 22 May 2017 their properties by filler, nucleation, dilution and chemical effects. The action mechanism of LS mainly
Received in revised form 8 June 2018 depends on its particle size and amount. The filler effect of LS refines the microstructure and reduces
Accepted 8 June 2018
the porosity of cement-based materials. Its nucleation effect accelerates the hydration of C3S, increases
the amount of hydration products and reduces the porosity of cement-based materials at early ages.
Its dilution effect reduces the hydration peak of C3S, decreases the amount of hydration products and
Keywords:
increases the porosity of cement-based materials. Its chemical effect promotes the appearance of third
Limestone powder
Action mechanism
hydration peak, forms carboaluminate and reduces the porosity of cement-based materials.
Hydration process Ó 2018 Elsevier Ltd. All rights reserved.
Hydration products
Microstructure

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
2. Action mechanism of limestone powder in cement-based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
2.1. Origin of limestone powder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
2.2. Filler effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
2.3. Nucleation effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
2.4. Dilution effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
2.5. Chemical effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
3. Hydration process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
3.1. Nucleation effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
3.2. Dilution effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
3.3. Chemical effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
4. Hydration products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
4.1. Nucleation effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
4.2. Dilution effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
4.3. Chemical effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664

⇑ Corresponding author.
E-mail address: cshi@hnu.edu.cn (C. Shi).

https://doi.org/10.1016/j.conbuildmat.2018.06.075
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
660 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672

5. Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
5.1. Filler effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
5.2. Nucleation effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
5.3. Dilution effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
5.4. Chemical effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
6. Summary and future needs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670

1. Introduction
According to data from the U.S. Geological Survey (USGS) in
2017, the world production of Portland cement was approximately
4.2 billion tons [1]. Production of 1 ton of cement clinker generates
approximately 0.87 ton of carbon dioxide [2]. Thus, production of
cement significantly increases the global carbon dioxide emissions.
Incorporation of supplementary cementitious materials (SCMs) is
an effective way to reduce the use of cement clinker and carbon
dioxide emissions. Moreover, the incorporation of SCMs would
not be detrimental to the mechanical properties and even
enhances the durability of the resulting concrete with a proper
mix design [3–5].
Limestone powder is a by-product of the limestone quarry, and
it has been used in cement-based materials for many years. In
1938, Bessey [6] first reported that CaCO3 could react with cement
to form calcium-carboaluminate. The formation of calcium-
carboaluminate was influenced by the amount and fineness of LS,
but it had little effect on the compressive strength of mixtures
[7]. In 1948, Deniels [8] claimed that the incorporation of LS
increased the compressive strength of concrete. Its filler effect
was later confirmed by an expert committee in Norwegian govern-
ment [9]. In 1976, Soroka and Setter [10] reported the accelerating
effect of LS on hydration of cement due to its nucleation effect.
Subsequently, a great number of studies were conducted on incor-
poration of LS in cement-based materials. It is now well-
documented that the presence of LS can promote the precipitation
of C-S-H and accelerate the hydration of cement [7]. The effects of
LS on the workability [11], strength [12–14], dimensional stability
[15,16] and durability [17,18] of concrete were also investigated.
Based on extensive research on application of LS in cement, the
European standard first introduced and defined Portland-
limestone cement in 1987, and allowed replacing Portland cement
with 15 ± 5% LS [19]. In 2000, the European standard (EN 197-1)
defined different type of Portland cement blends with LS [20],
and the allowable replacement level increased to 35% [20]. In
2008, the Canadian standard (CSA A3001-08 [21]) also introduced
Portland-limestone cement with LS contents below 15% of total
binder. Subsequently, Portland-limestone cement was designated
as GUL (general use limestone cement) in CSA A3001-10 [22]. In
2012, ASTM C595 [23] also introduced Portland-limestone cement
with LS up to 15%.
Many researchers have conducted studies on LS in cement-
based materials. This paper reviews the action mechanisms, hydra-
tion and microstructures of cement-based materials containing LS.
The aim of this review is to summarize previous research progress
and to suggest some needs for future studies.
two broad mechanisms of filler effect (including filler effect, nucle-
ation effect and dilution effect) and chemical effect, while other
specified filler effect, nucleation effect, dilution effect and chemical
effect as distinctive mechanisms [27–30]. Thus, it is necessary to
clarify the action mechanisms of LS in cement-based materials
before discussing the effects of LS on the hydration and microstruc-
ture of cement-based materials. In order to define the action mech-
anisms of LS in cement-based materials, in this paper, they are
classified as filler effect, nucleation effect, dilution effect and chem-
ical effect.
2.1. Origin of limestone powder
Limestone powder is crushed and ground from natural lime-
stone. Belsazar Hacquet [31] first distinguished limestone from
dolomite as sedimentary rock. Limestone is mainly composed of
skeletal fragment of organisms. Calcite, aragonite, vaterite and
amorphous calcium carbonate are the available forms of mineral
composition of limestone. Limestone can be formed from marine
organisms, lacustrine [32] and evaporite depositional environ-
ments [33,34]. It can also be formed from chemical precipitation
of calcite or aragonite. Based on the method of formation, LS could
be crystalline, clastic, granular or massive.
2.2. Filler effect
The filler effect of LS is mainly related to its particle size. The
calculated packing density of mixtures containing cement, slag
and LS is illustrated in Fig. 1 [25]. It can be seen from Fig. 1(a) that
the packing density of mixtures is lower when the particle size of
LS is coarser or comparable to Portland cement, whereas the pack-
ing density is higher when the particle size of LS is finer than that
of cement as shown in Fig. 1(b). Therefore, if the particle size of LS
is finer than cement particle, incorporation of LS will fill the voids
between cement particles and improve the particle size distribu-
tion and finally increase the packing density of cement-based
materials [35]. As a result, the incorporation of LS reduced the
water requirement of concrete and increased the compressive
strength and durability of concrete [24]. Although the incorpora-
tion of fine LS could fill the void between cement particle, the
incorporation of LS will reduce the flowability of cement-based
materials if the particle size of LS was too small since its specific
surface area was high. The flowability of UHPC decreased by 27%
when 3% nanolimestone was incorporated into UHPC [36].
2.3. Nucleation effect

2. Action mechanism of limestone powder in cement-based Since Soroka and Setter [10] first introduced the nucleation
materials effect of LS, many researchers have confirmed that fine LS provides
nucleation sites for hydration products to precipitate [37], acceler-
Different mechanisms were used to explain the action mecha- ates the hydration reaction [38], and improves the hydration
nism of LS in cement-based materials. Some scholars [24–26] degree of cement [24]. It was reported that the enhanced precipi-
divided the action mechanism of LS in cement-based materials into tation of C-S-H on the surface of LS was due to similarity between
 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672
Fig. 1. Calculated packing density of mixtures containing cement, slag, and LS: (a) coarse LS, (b) fine LS [25].
planar configuration of Ca and O atoms in calcite and CaO layers in
C-S-H [39].
The particle size [40], surface structures [41] and amount of LS
[42] influence the nucleation effect of LS. The surface energy and
absorption capacity of LS particles increases as its particle size
decreases. The hydration products of cement tend to envelop the
surface of LS particles with similar surface structures which refer
to Ca and O atoms in calcite and CaO layers in C-S-H. Since the
physical and chemical of nanomaterials is unstable, the nucleation
effect of nanolimestone was more pronounced, and the hydration
peak of UHPC with 2% nanolimestone reduced by 1.3 h compared
with UHPC without nanolimestone [36]. With the increase of LS
amount, more nucleation sites would be available, and more
hydration products could be absorbed. However, it is unclear that
which factors are dominant in the nucleation effect of LS.
2.4. Dilution effect
The dilution effect of LS is mainly attributed to its amount in the
matrix. As the alumina presents in cement in minor amount, only a
small fraction of LS take part into the reactions. Therefore, incorpo-
ration of a larger fraction of LS as a substitution to cement
decreases the content of cement clinker and the hydration prod-
ucts. Moreover, with the same water/binder ratio, since LS does
not have cementitious or pozzolanic properties, its replacement
with cement increase the free water to react with cement particles,
which is known as dilution effect. As a result, the hydration degree
of cement increases, which has been confirmed in many studies
[24,25,28,29].
2.5. Chemical effect
The chemical effect of LS on the mixture is mainly influenced by
its particle size, the content of alumina from C3A and C4AF in
cement as well as SCMs. With the increase of particle size of LS,
the dissolution rate of LS increases. As a result, the concentration
of calcium carbonate in pore solution increases, which promotes
the chemical effect of LS. Especially for nanolimestone, with the
decrease of particle size of nanolimestone, its surface energy and
surface morphology change remarkably, and the chemical reactiv-
ity of LS also increases. On the other hand, the C3A, C4AF and SCMs
could provide aluminate sources, which also enhance the chemical
reaction of LS. The stabilization of ettringite was reported as the
661
redundant C3A and C4AF reacted with carbonate ion from LS to
form carboaluminate [43–45]. The incorporation of LS also chan-
ged the morphology of C-S-H into shorter and thicker fibers of C-
S-H (I) [46]. As the aluminate phase in cement clinker is limited,
the chemical effect of LS in cement-based materials is small. The
additional aluminate in SCMs could increase the chemical effect
of LS [47].
It should be noted that previous studies reported inconsistent
results on the chemical reaction of LS. On one hand, it was reported
that LS reacted with C3A in cement, and the alkalinity of cement-
based materials reduced. The associated reaction equations are
shown as Eqs. (1) and (2) [43]. It was also reported that LS reacted
with C3A in cement but didn’t influence the alkalinity of cement-
based materials. The reaction equations are shown as Eqs. (3)
and (4) [48]. On the other hand, it was reported that LS reacted
with calcium sulphoaluminate and increased the alkalinity of
cement-based materials. The reaction equations are shown as
Eqs. (5) and (6) [49]. Elsewhere, LS reacted with calcium
sulphoaluminate and the reaction decreased the alkalinity of
cement-based materials as shown by Eqs. (7) and (8) [50]. From
Eqs. (1)–(8), it can be seen that the chemical effects of LS might
influence the alkalinity, humidity, volume stability of the matrixes,
thus, great importance should be attached to clarification of the
chemical reaction of LS in cement-based materials.

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 ! 285 cm3 =mol; DV ¼ 130 Vol% ð1Þ
 
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% ð2Þ

3C 3 A þ 0:5C C þ18H

! C 3 A  CC 0:5  H12 þ 2AH3 3  89 cm3 =mol þ 0:5  37cm3 =mol
! 285 cm3 =mol þ 2  33 cm3 =mol; DV ¼ 23 Vol% ð3Þ

3C 3 A þ C C þ17H

! C 3 A  C C H11 þ 2AH3 3  89 cm3 =mol þ 37 cm3 =mol
! 262 cm3 =mol þ 2  33 cm3 =mol; DV ¼ 8 Vol% ð4Þ
662 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672

 
6C 4 A3 S þC C þ135H mixture incorporating fine LS. With the increase of particle size
  of LS, the heat release curves became similar to that of the OPC
! 2C 4 AC 0:5 H12 þ 2C 3 A  3C S H32 þ 14AH3 mixture. It was reported that the nucleation effect of finer LS could
þ 5CH6  309 cm3 =mol þ 37 cm3 =mol promote the precipitation of hydration products, and increase the
hydration degree of cement, as a result, more hydration heat
! 2  285 cm3 =mol þ 2  707 cm3 =mol þ 14  33 cm3 =mol
released [51].
þ 5  33 cm3 =mol; DV ¼ 38 Vol% ð5Þ With the increase of amount of fine LS at a constant maximum
particle size (i.e., 5 lm), the rate of hydration increased, and the
 
3C 4 A3 S þ2C C þ72H total hydration heat of mixtures was higher than that of the Port-
  land cement mixture for LS amount below 10%, as shown in Fig. 3
! 2C 4 A C H11 þ C 3 A  3C S H32 þ 6AH3 3  309 cm3 =mol [42]. More LS particles provided more nucleation sites. As a result,
þ 2  37 cm3 =mol ! 2  262 cm3 =mol þ 707 cm3 =mol the hydration degree and hydration heat of cement-based materi-
als increased with the increase of amount of LS.
þ 6  33 cm3 =mol; DV ¼ 43 Vol% ð6Þ
In order to compare the effects of different polymorphs of cal-
  cium carbonate on the hydration process of cement-based materi-
3C 4 A3 S H12 þ CH þ C C þ19H als, the effects of aragonite (Sturcal F limestone) and calcite
  (Marblewhite limestone and HT Sturcal F limestone) on the hydra-
! C 6 AS3 H32 þ 2C 4 AC 0:5 H12 3  309 cm3 =mol þ 33 cm3 =mol
tion process of cement-based materials were investigated [41]. It
þ 37 cm3 =mol ! 707 cm3 =mol þ 2  285 cm3 =mol; DV can be seen that from Fig. 4 [41] that calcite accelerated and ampli-
¼ 28 Vol% ð7Þ fied the silicate reactions, while aragonite had less effect on the
peak related to silicate reaction. This can be related to the different
  surface structures of calcite and aragonite in aqueous solutions
3C 4 A3 S H12 þ 2C C þ18H
[39,52]. The surface of calcite is composed of a planar configuration
 
! C 6 AS3 H32 þ 2C 4 A C H11 3  309 cm3 =mol þ 2  37 cm3 =mol of Ca and O atoms, which is similar to the CaO layers in C–S–H. The
spacing of the calcium atoms in the grid of calcite (10 14) cleavage
! 707 cm3 =mol þ 2  262 cm3 =mol; DV ¼ 23 Vol% ð8Þ
plane is 0.5 nm by 0.4 nm [39], which resembles the CaO layers in
tobermorite (0.56 nm by 0.36 nm) [47]. By contrast, only Ca atoms
3. Hydration process were found on the surface layer of aragonite whereas no O atoms
were detected [52]. As a result, the surface of calcite was more con-
As the filler effect of LS has negligible influence on the hydration ducive to the precipitation and growth of early-age hydration
process of cement-based materials, this section only discusses the products than that of aragonite [41].
nucleation, dilution and chemical effect of LS on the hydration pro-
cess of cement-based materials. 3.2. Dilution effect

The dilution effect of LS on hydration process of cement-based

3.1. Nucleation effect
materials is mainly influenced by its amount, especially when the
LS with coarse particles size are used. When coarse LS (maximum
The nucleation effect of LS on hydration process of cement-
particle size = 20 lm) was incorporated into cement, there was no
based materials is mainly influenced by its particle size, amount
significant difference between the heat evolution curves of the pure
and surface structures. As shown in Fig. 2 [40], the main hydration
Portland cement mixture and Portland cement blending with LS, as
peak of sample containing the finest LS (i.e., median particle size =
shown in Fig. 5 [42]. Moreover, the maximum heat of hydration for
0.7 lm) was 15% higher than that of the OPC sample, and it
Portland cement mixture was approximately 3.0 mW/g, and it
appeared 25% prior to that of the OPC mixture. A more pronounced
decreased with the increase of LS amount. It can be seen from
shoulder on the main hydration peak could be observed for the
Fig. 5(b) that the 48 h total hydration heat of mixtures containing
coarse LS were lower than that of pure Portland cement mixture,
and it tended to decrease with the increase of LS amount [42].

3.3. Chemical effect

The chemical effect of LS on hydration process of cement-based

Fig. 2. Influence of particle size of LS on the heat release rate [40].
materials is mainly influenced by its particle size and its synergic
effect with SCMs. With the decrease of LS particle size, the dissolu-
tion of calcium carbonate increased, and the chemical reaction
between calcium carbonate and aluminate enhanced. It can be
seen in Fig. 2 that with the decrease of particle size of LS, a double
dump appeared in the curve of heat release rate, which could be
attributed to the formation of carboaluminate [40].
Although the chemical effect of LS is little since the aluminate
phase in cement is limited, the additional aluminate phase from
SCMs could enhance the chemical effect of LS. It could be observed
in Fig. 6 [53] that the cumulative heat of hydration of mixtures
containing slag and/or LS was generally lower than that of the
OPC mixture. Nevertheless, the cumulative heat of hydration of
mixtures was not proportional to the cement replacement level,
which could be attributed to the formation of the monocarbonate
phase. Comparing with mixture containing slag alone, the
 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672 663

Fig. 3. Heat of hydration of PC–5 lm LS; (a) heat evolution and (b) total heat evolved [42].

Fig. 4. Isothermal heat flow as a function of time at 23 °C for Type III cement/F ash with and without various CaCO3 replacements [41].

cumulative heat of hydration of mixtures containing both LS and
slag were higher. It indicated that the reactivity of LS increased
in the presence of slag [53].
From Table 1, it can be seen that incorporating proper fine lime-
stone powder mainly displays nucleation effect, accelerates the
hydration of C3S, increases the hydration peak of C3S and hydration
heat of cement-based materials. However, it may also decrease the
hydration peak of C3S and hydration heat of cement-based materi-
als if ultra- fine limestone powder or coarse limestone powder in
incorporated, which dominates the dilution effect. The additional
aluminate phase from SCMs enhances the chemical effect of lime-
stone powder, promotes the formation of carboaluminate and
increases the hydration heat of cement-based materials.
4. Hydration products
It is well-known that the main hydration products of cement-
based materials without LS are calcium silicate hydrate (C-S-H),
ettringite, monosulfate and calcium hydroxide, etc. The incorpora-
tion of LS in Portland cement resulted in additional formation of
hemi- and/or mono-carbonate instead of the monosulfate
[43–45]. Moreover, slightly more ettringite was formed when LS
was incorporated into cementitious materials [54]. Since the filler
effect of LS has little influence on the hydration products of
cement-based materials, the nucleation, dilution and chemical
effect of LS on the hydration products of cement-based materials
are discussed in this section.
4.1. Nucleation effect
The nucleation effect of LS on hydration products of cement-
based materials is influenced by its particle size. The non-
evaporable water content (Wn) could be potentially used as an
indicator to estimate the hydration degree of cement-based
materials. The non-evaporable water content of mixtures at 3
and 28 days were investigated, as shown in Fig. 7 [53]. It could
664 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672

Fig. 5. Heat of hydration of PC–20 lm LS; (a) heat evolution and (b) total heat evolved [42].

LS. In comparison, the normalized CH contents of mixtures con-

taining 0.7 lm and 3 lm LS were higher at 1 day [40].

4.2. Dilution effect

The dilution effect of LS on hydration products of cement-based

materials is mainly influenced by its amount. The effects of differ-
ent mineral powders, such as LS and quartz powder, on the hydra-
tion products of cement-based materials were investigated in [55].
Although the hydration degree of mixtures containing mineral
powders was higher, the CH content was slightly lower because
the cement clinker was relatively low, especially for the mixtures
containing 30% and 40% mineral powders at 1 day. A higher
replacement of cement notably reduced the CH content.

4.3. Chemical effect

The chemical effect of LS on hydration products of cement-

Fig. 6. Cumulative heat of hydration in W/g of binder (cement + slag) for: (a)
volumetric replacement of OPC by slag (OPC-20: 80%OPC + 20% slag by volumetric
percentage), (b) OPC replaced by LS–slag blends (BLD-20: 80%OPC + 7.3% slag +
12.7% LS, BLD-40: 60%OPC + 27.3% slag + 12.7% LS by volumetric percentage) [53].
be observed that the Wn of OPC–slag–LS interground mixtures
were higher than that of OPC–slag and OPC–slag–LS blended mix-
tures at 3 days, but the incorporation of LS had little effect on the
Wn of cement-based materials at 28 days. It might be attributed
to the nucleation effect of LS that improved the hydration degree
of cement-based materials at early ages. The effect of particle size
of LS on the normalized CH content of was also investigated. The
normalized CH content (CH content per gram cement) of mixture
containing 15 lm LS was similar to that of the mixtures without
based materials is mainly influenced by its particle size and
amount and its synergic effect with SCMs. The XRD data presented
in Fig. 8 [43] shows that the aluminate phase reacted with CaCO3 to
form mono- and hemi-carbonate when LS was incorporated into
cement-based materials [43]. The peak corresponding to hemicar-
bonate was observed after 7 days. Later, the peak of hemicarbonate
decreased but the peak of monocarbonate increased. Ipavec et al.
[56] also found that calcium hemicarboaluminate was formed at
early ages in OPC blend containing LS, and it was converted into
calcium monocarboaluminate after 28 days. However, it was also
reported [57] that the hydration degree of limestone powder was
very low at early ages, and the calcium monocarboaluminte
hydrates was detected at 180 days.
In order to clarify the influence of particle size of LS on its chem-
ical effect, the normalized CH contents of mixtures with intergrind-
ing or blending LS were investigated, as shown in Fig. 9 [53].
Intergrinding or blending LS had little effect on the normalized
CH contents of mixtures. The chemical effect of LS in cement-
based materials was also assessed by quantifying the consumption
of carbonate. The consumed carbonate content in the blended and

Table 1
Effects of limestone powder on the hydration process of cement-based materials [40,42,53].

Binder composition (%) Particle size (lm) Replacement pattern Main action mechanism
90%OPC + 10%LS Medial particle size: 0.7, 3, 15 Replacing cement Nucleation effect [40]
(70–100%)OPC + (0–30%)LS Maximum particle size: 5, 20 Replacing cement Dilution effect [42]
(50–100%)OPC + (7.3–50%)Slag + (0–12.7%)LS Medial particle size: 0.7, 3, 10, 15 Replacing slag Chemical effect [53]
 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672 665

Fig. 7. Non-evaporable water content normalized with respect to clinker factor as a function of the clinker replacement level at: (a) 3 days and (b) 28 days. OPC:OPC + slag,
BLD: OPC blending with LS + slag, INT: OPC intergrinding with LS + slag [53].

Fig. 8. XRD-patterns for the different tested blends at 1, 7, 28, 90 and 180 days. The main peaks of ettringite (E), monosulphate (Ms), possibly a sulphate and carbonate
containing hydroxy-AFm(AFm*), hemicarbonate (Hc), monocarbonate (Mc) and ferrite (F) were observed [43].

Fig. 9. Normalized CH content with respect to clinker factor plotted as a function of the clinker replacement level at: (a) 3 days and (b) 28 days [53].
666 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672

Fig. 10. Normalized consumed carbonate content with respect to clinker factor plotted as a function of the clinker replacement level at: (a) 3 days and (b) 28 days [53].

interground OPC-LS-slag systems after 3 and 28 days is shown in during the thermal analysis, the residual calcium carbonate will
Fig. 10 [53]. It can be observed in Fig. 10(a) that, within 3 days, increase, and thus, the consumption of calcium carboaluminate
more than 10% of the carbonates in interground OPC-LS-slag mix- would be underestimated.
tures were consumed while the consumption in the blended OPC- 
TP111 C
 
LS-slag mixtures was around 5%. It might be attributed to the finer C 6 A S H32 ƒƒƒƒƒ! C 4 A S H12 þ C S H0:5 þ H " ð9Þ
particle size of LS in the interground OPC-LS-slag mixtures. How-
 
TP190 C
ever, the carbonate consumption at 28 days was similar in the C 4 A S H12 ƒƒƒƒƒ! C 3 AH6 þ C S þH " ð10Þ
interground OPC-limestone powder-slag mixtures and blended
OPC-limestone powder-slag mixtures. The delayed reaction and TP280 C
C 3 AH6 ƒƒƒƒƒ! C 4 A3 H3 þ CH þ H " ð11Þ
higher consumption rate of limestone powder at later ages may
be explicated with the coarser and less reactive particles of LS Both calcium hydroxide and carboaluminate content could be
when it came to reaction with aluminate phases. It is worth saying influenced by the amount of LS. Incorporating LS to replace 5% of
that before quantifying the consumption of carbonate phases, the OPC decreased the normalized CH content after 7 days. Incorporat-
thermal decomposition reaction of calcium carboaluminate should ing LS to replace 5% of fly ash in OPC-FA mixture also decreased the
be clarified. It was reported [58] that calcium sulphoaluminate was normalized CH content after 28 days. The decrease in CH content
decomposed under thermal condition, as shown in Eqs. (9)–(11). indicated that the formation of calcium hemicarboaluminate
The molecular structure of calcium carboaluminate is similar with hydrate could consume CH [43]. The effect of amount of LS on
calcium sulphoaluminate. If the calcium carbonate is regenerated the carboaluminate content of cement-based materials was also

Fig. 11. Influence of different quantities of LS on the hydration of cements: (a) C3.5-1, (b) C3.5-3, and (c) C3.5-9. The main peaks of ettringite (Et), hemicarbonate (Hc),
monocarbonate (Mc) and ferrite phase (C4AF) were observed [59].
 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672
Fig. 12. Thermal gravimetric analyses of cement pastes hydrated at 90 days [64].
investigated [59]. It can be observed in Fig. 11 [59] that the inten-
sity of hemicarbonate peak of cement-based materials containing
3% LS (C3.5-3) and 9% LS (C3.5-9) was higher than that of
cement-based materials containing 1% LS (C3.5-1). For the
cement-based materials containing 1% LS (C3.5-1), the formation
of monocarbonate was delayed, and a broad peak at 2h  11.3°
was observed, which was probably corresponding to a composition
between hemicarbonate and monocarbonate [60]. The monocar-
bonate gradually increased with time in all samples, and the rate
of monocarbonate formation was the lowest for the cement-
based materials containing 1% LS (C3.5-1) [59].
The synergic effect between LS and SCMs also influences the
hydration products of cement-based materials containing LS. By
determining the carbonate consumption or hemi/mono-
carbonate content, the synergistic effect between LS and slag could
be quantified [61]. With the increase of cement clinker replace-
ment level, the carbonate consumption increased. With the
increase of carbonate consumption, the hemi- and mono-
carbonate content increased. The reason might be that the reactive
alumina in slag (8.7%) increased the reactivity of LS [53]. In the
presence of the calcium aluminosilicate (CAS) glasses, the chemical
effect of LS also increased [62]. As shown in Fig. 12 [62], the reac-
tion ratio of LS in the mixture containing 30% of LS was 9%, whereas
it increased to 16% as CAS9N replaced with 10% LS. The reason
might be the relatively high Al2O3 content in the CAS glasses. It
was also supported by previous studies that a higher C3A content
increased the carbonate consumption in Portland limestone
cements [63,64]. Although the reactive alumina in SCMs could
increase the chemical effect of LS, it was reported that the reaction
ratio of fly ash and slag after one year were approximately 25–30
wt% and 70 wt%, respectively [65,66], and thus the formation of
hemi/mono-carbonate was limited. It was confirmed by previous
study that the Al2O3 content in fly ash and slag used was 18.5%
and 7.9%, respectively [50]. Due to the lower activity of slag and
fly ash, the actual reaction content of Al2O3 in fly ash and slag with
LS was approximate 5% and 5.5%, respectively. As a result, the
effects of slag and fly ash on the formation of hemi- and mono-
carbonate in cement-based materials containing LS were limited
[50].
Table 2
Effects of limestone powder on the hydration products of cement-based materials [40,43,53,55,59].
Binder composition (%) Particle size (lm)
90%OPC + 10%LS Medial particle size: 0.7, 3, 15
(50–100%)OPC + (7.3–50%)Slag + (0–12.7%)LS Medial particle size: 0.7, 3, 10, 15
(60–100%)OPC + (0–40%)LS / Replacing
(65–100%)OPC + (0–35%)FA + (0–5%)LS Medial particle size: 4
(91–99%)OPC + (1–9%)LS Medial particle size: 8
667
Fig. 13. Pore size distribution of mixtures with 350 kg/m3 of cement [74].
From Table 2, it can be concluded that it would mainly show
nucleation effect if proper fine limestone powder was incorporated
into cement-based materials, and the hydration degree of cement
would increase, thus more C-S-H and CH were formed at early
ages. However, the nucleation effect of limestone powder had little
effect on the hydration products at later age. It would mainly dis-
play dilution effect if superfluous fine limestone powder or coarse
limestone powder was incorporated into cement-based materials,
thus less C-S-H and CH were formed. The chemical effect of lime-
stone powder on hydration products of cement-based materials
is mainly originated from the reaction between limestone powder
and alumina in cement-based materials and it generates carboalu-
minate. More carboaluminate would formed at early ages when
fine limestone powder was incorporated, but the content of car-
boaluminate is similar at later age regardless of the particle size
of limestone powder. More carboaluminate would formed if the
amount of limestone powder increased or SCMs containing Al2O3
was also incorporated.
5. Microstructure
In general, the LS particles can solidify the microstructure of
cement-based materials in different fashions. Fine LS particle could
fill the pores between hydration products. The nucleation effect of
LS could improve the hydration degree of cement and generate
more hydration products at early ages. The dilution effect of LS
can decrease the reactive cement clinker and reduce the amount
of hydration products. The chemical effect of LS can increase the
volume of solid phase of hydration products. Thus, all the four
effects influence the microstructure of cement-based materials.
5.1. Filler effect
The filler effect of LS on the microstructure of cement-based
materials is mainly influenced by its particle size and amount. A
refined pore structure was obtained when fine LS was incorporated
in the mixture comparing to plain Portland cement mortar [67].
Replacement pattern Main action mechanism
Replacing cement Nucleation effect [40]
Replacing slag Nucleation effect [53]
cement Dilution effect [55]
Replacing cement Chemical effect [43]
Replacing cement Chemical effect [59]
668 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672

The mean pore size of mortar with plain Portland cement was
60 nm, while the mean pore size of mortar containing 10% LS
was 31 nm [68]. The refining effect of LS was further improved
by decreasing its particle size [69,70]. Incorporating proper
amount of fine limestone powder reduced the volume of large pore
and increased the volume of small pores with diameter smaller
than 100 nm, which had little harm to the properties of
cement-based materials [71,72]. Li et al. [73] also found that the
nano-limestone particles effectively filled pores of ultra-high per-
formance concrete and a denser matrix was obtained comparing
to plain specimens.
When LS was incorporated to replace the aggregate without
change the cement and water content, the threshold pore diameter
of S-350/90 (Cement: 350 kg/m3, LS: 90 kg/m3) was lower than
that of S-350/0 (Cement: 350 kg/m3, LS: 0 kg/m3) and S-350/45
(Cement: 350 kg/m3, LS: 45 kg/m3), as can be seen from Fig. 13

Fig. 14. SEM results of C3S control (left) and C3S + nano-CaCO3 (right), hydrated for (a, b) 0 h, (c, d) 2 h, (e, f) 4 h, (g, h) 1 day, and (i, j) 3 days. [76].
 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672
Fig. 14 (continued)
[74]. Moreover, the volume of large capillary pores and
macro-pores in S-350/90 was 35.2% and 31.7% less than that
of S-350/0 and S-350/45, respectively. Incorporation of LS to
replace the aggregate filled the pores and reduced the porosity of
mixtures [74].
5.2. Nucleation effect
The nucleation effect of LS accelerated the hydration of cement,
promoted the precipitation of C-S-H, and filled the pores in mix-
tures at early ages [75]. During the hydration process of cement,
the SEM results of cement-based materials without and with lime-
stone powder were observed as shown in Fig. 14 [41,76]. For the
control group, it was observed that a few fibrous C-S-H appeared
on the surface of C3S at 2 h, while the fibrous C-S-H appeared on
the surface of CaCO3 [76]. It was also observed that a large amount
of ordered materials precipitated on the surface of LS, and they
were consistent with the calcite cleavage surface through atomic
force microscope observation [39]. During the first 15 min, it was
Fig. 15. Porosity and average pore size of blended binder pastes after 28 days of
hydration [78].
Table 3
Effects of limestone powder on the microstructure of cement-based materials [41,43,74,78].
Binder composition (%) Particle size (lm)
100%OPC / Replacing
90%OPC + 10%LS Medial particle size: 1.6, 16
(65–100%)OPC + (0–35%)LS Medial particle size: 3, 10
(65–100%)OPC + (0–35%)FA + (0–5%)LS Medial particle size: 4
669
observed that etched pits were formed [77]. Subsequently, C-S-H
was precipitated in the etch pits during the hydration process of
cement [76].
5.3. Dilution effect
When enough coarse LS was incorporated into cement-based
materials, the porosity of mixtures was higher than that of control
OPC mixture, as shown in Fig. 15 [78]. Since the particle size of LS
used was close to cement, the average pore size of mixtures with
LS was similar to that of control OPC mixtures.
5.4. Chemical effect
Since LS stabilizes the ettringite and react with aluminate phase
in cement and supplementary cementitious materials to form
hemi- and mono-carboaluminate, the chemical effect of LS can
influence the porosity of mixtures containing LS. As shown in
Eqs. (1)–(8), the chemical effect of LS can increase the solid volume
of hydration products, and reduce the porosity of cement-based
materials. Reportedly, ettringite decomposed into monosulphate
in the absence of LS [43]. When LS was incorporated into
cement-based materials, the decomposition of ettringite was pre-
vented, and calcium hemi- and mono-carboaluminate were
formed. At 25 °C, the molar volume of ettringite and monosulphate
was 707 cm3/mol and 309 cm3/mol, respectively. Ettringite was
more voluminous than monosulphate [79]. Thus, when suitable
LS was added into mixtures, the porosity of mixtures reduced [43].
From Table 3, it is easy to inferred that it would mainly show
filler effect when suitable fine limestone powder was used, and it
would refine the pore structure and reduce the porosity of
cement-based materials. It would mainly display nucleation effect
if proper fine limestone powder was incorporated into cement-
based materials, and the porosity of cement-based materials
decreased at early ages. It would mainly display dilution effect if
superfluous fine limestone powder or coarse limestone powder
was incorporated into cement-based materials, thus increased
the porosity of cement-based materials. The chemical effect
of limestone powder generates carboaluminate, stabilizes the
ettringite and thus reduce the porosity of cement-based materials.
Replacement pattern Main action mechanism
aggregate Filler effect [74]
Replacing cement Nucleation effect [41]
Replacing cement Dilution effect [78]
Replacing cement Chemical effect [43]
670 D. Wang et al. / Construction and Building Materials 181 (2018) 659–672
6. Summary and future needs
Based on the above discussions, the following conclusions can
be drawn:
(1) LS influences the properties of cement-based materials by its
filler effect, nucleation effect, dilution effect and chemical
effect. Incorporating proper fine limestone powder acceler-
ates the hydration of C3S, increases the hydration peak of
C3S and hydration heat of cement-based materials. However,
it decreases the hydration peak of C3S and hydration heat of
cement-based materials if superfluous fine limestone pow-
der or coarse limestone powder is incorporated. The alumi-
nate phase in C3A, C4AF and SCMs promotes the formation
of carboaluminate and increases the hydration heat of
cement-based materials. In the absence of LS, ettringite
decomposes into monosulphate. Incorporation of LS pre-
vents the decomposition of ettringite to monosulphate.
Incorporating suitable fine limestone powder increases the
hydration degree, generates more C-S-H and CH at early
ages, but it has little effect on the hydration products at later
age. Incorporating superfluous fine or coarse limestone
powder generates less C-S-H and CH. The chemical effect
of limestone powder generates carboaluminate. More car-
boaluminate would formed at early ages if fine limestone
powder was incorporated, but the content of carboalumi-
nate is similar at later age regardless of the particle size of
limestone powder. More carboaluminate would formed if
the amount of limestone powder increased or SCMs contain-
ing Al2O3 was also incorporated.
(2) Incorporating suitable fine limestone powder refines the
pore structure and reduces the porosity of cement-based
materials due to filler and nucleation effects. Incorporating
superfluous fine limestone powder or coarse limestone pow-
der increases the porosity of cement-based materials due to
dilution effect. The chemical effect of limestone powder gen-
erates carboaluminate, stabilizes the ettringite and thus
reduces the porosity of cement-based materials.
(3) The filler effect of limestone powder has little effect on the
hydration of cement-based materials. Its nucleation effect
mainly accelerates the hydration peak of C3S and generates
more hydration products at early ages. The dilution effect
of LS reduces the hydration peak of C3S and decreases the
content of C-S-H and Ca(OH)2. Its chemical effect reflects
at the third peak which corresponds to the formation of
carboaluminate.
(4) The effects of limestone powder on the microstructure of
cement-based materials is complex and cannot clarify
directly. The filler effect of limestone powder on the
microstructure of cement-based materials might be
reflected by the residual content of limestone powder; its
nucleation effect might be clarified by the relative content
of C-S-H and Ca(OH)2 at early age; its dilution effect might
be clarified by the relative content of C-S-H and Ca(OH)2 at
later ages; its chemical effect could be verified by the
content of consumed limestone powder or formation of
carboaluminate.
(5) To reduce the porosity and improve the durability of
cement-based materials, using less than 10% fine limestone
powder to replace cement is recommended, and it mainly
shows the desirable filler, nucleation and chemical effects.
Moreover, incorporating limestone powder and slag/fly ash
shows synergistic effect in favor of further reduction of the
porosity and improvement of the durability of cement-
based materials.
The effects of LS on the hydration and microstructure of
cement-based materials depend on many factors. In order to clarify
the effects of LS in cement-based materials, some further research
needs to be conducted:
(1) Although the filler effect, nucleation effect, dilution effect
and chemical effect of LS on the hydration and microstruc-
ture of cement-based materials have been intensively inves-
tigated, the extent to which these effects influence the rate
of hydration, heat of hydration, hydration products and pore
structure characteristics of cement-based materials still
need further study.
(2) It is widely accepted that hemi- and mono-carbonate are
formed when LS is incorporated into cement-based materi-
als. The reason why metastable hemicarbonate phase is
formed instead of direct formation of mono-carbonate need
to be further investigated. Moreover, the chemical reaction
equation of LS in cement-based materials needs to be
clarified.
(3) Limited research is available on the carbonate consumption
of LS. It is assumed that aluminates in cement or supplemen-
tary cementitious materials could increase the consumption
of LS. In order to quantify the consumption of carbonate
by thermogravimetric analysis, it may be necessary to
clarify the thermal decomposition reaction of calcium
carboaluminate.
(4) LS could react with aluminate phase in cement or supple-
mentary cementitious materials to form calcium mono- or
hemi-carboaluminate and consequently stabilize the
ettringite. The formations of calcium mono- or hemi-
carboaluminate increase the solid volume of hydration
products, and the molar volume of ettringite is larger than
that of monosulphate. Hence, the associated hydration prod-
ucts may fill the pore of cement-based materials or cause
cracking. The effect of these hydration products on the
microstructure of cement-based materials need to be further
investigated.
Conflict of interest
The authors declare that there is no conflict of interest.
Acknowledgements
Financial supports from National Science Foundation of China
under contract Nos. 51608187 and 51461135001 are greatly
appreciated. The project was also supported by Key Laboratory of
Advanced Civil Engineering Materials (Tongji University), Ministry
of Education (No. 201702) and State Key Laboratory of High Perfor-
mance Civil Engineering Materials (No. 2016CEM006).
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