Construction and Building Materials 188 (2018) 1045–1049

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Construction and Building Materials

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

Effect of limestone powder in manufactured sand on the hydration

products and microstructure of recycled aggregate concrete
Haifeng Yang a,b, Dongyao Liang a,b, Zhiheng Deng a,b, Yinghong Qin a,b,⇑
a
Guangxi Key Laboratory of Disaster Prevention and Structural Safety, College of Civil Engineering and Architecture, Guangxi University, Nanning 530004, China
b
Key Laboratory of Disaster Prevention and Structural Safety of Ministry of Education, Guangxi University, Nanning 530004, China

h i g h l i g h t s

Only a small quantity of limestone power (LP) reacts during hydration.

LP improves the compactness of the cement matrix and the ITZ.

LP does not change the composition of hydration products but varied its morphology.

LP sets seeds for nucleating new hydration products and accelerates the hydration.

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

Article history: In this paper, X ray diffraction test and Scanning electron microscope test were designed to investigate
Received 16 March 2018 the effect of limestone powder (LP) in manufactured sand on the hydration products and microstructure
Received in revised form 21 August 2018 of full recycled coarse aggregate concrete samples. The results showed that most of LP was inactive,
Accepted 23 August 2018
except only a small quantity of LP participated in the hydrating reaction at mid-late period. This small
amount of LP did not change the composition of hydration products but varied their morphology.
Some amount of LP filled in the pore structure of cement matrix and in the interface between recycled
Keywords:
coarse aggregate and new harden cement paste, improving the compactness of the cement matrix and
Limestone powder
Manufactured sand
the interfacial transition zone. The nucleation around the LP who filled in the pore structures was also
Recycled coarse aggregate observed, and the hydration products gradually formed and subsided on the surface of these LP and accel-
Hydration product erated the cement hydration.
Microstructure Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction feasible to produce concrete by using MS in the place of natural

Manufactured sand (MS) is a by–product of crushing rock as
natural aggregate, mixing with different levels of LP whose particle
diameter is less than 75 lm during the crushing process [1–3].
Replacing river sand with MS retards the depletion of the natural
fine aggregate. Properties, such as mixing proportion [4], workabil-
ity [1,5], mechanical behaviors [6–8] and others [9,10], of concrete
containing MS thus have been an important topic in the world-
wide. It has been found that the workability and compressive
strength of MS-included concrete were comparable with those of
natural fine aggregate concrete [6,8]. Compared to concrete con-
taining natural sand, a lower water-to-cement ratio and a greater
amount of water-reducing agent may be needed [5,11]. It is thus
⇑ Corresponding author at: Guangxi Key Laboratory of Disaster Prevention and
Structural Safety, College of Civil Engineering and Architecture, Guangxi University,
Nanning 530004, China.
E-mail address: yqin1@mtu.edu (Y. Qin).
sand [2,3].
Considering that the stone powder in MS maybe affect the
behaviors of concrete, some researchers focused on the influence
of stone powder content on the properties of concrete containing
MS [6,12–14]. It is found that the stone powder increased the com-
pressive strength of concrete with a small percentages (less
than10%) of powder in MS. Once the powder content exceeded
10%–20% mass percentage, the compressive strength decreased
with the increase of the stone powder level.
On the other hand, recycling demolished waste concrete as
coarse aggregate is also became an international consensus nowa-
days [15–18]. Thus, it is a breakthrough to adopt the MS and recy-
cled coarse aggregate (RCA) simultaneously to reproduce new
concrete in order to meet the sustainable development of building
materials. However, it is generally considered that some draw-
backs of recycled coarse aggregate, such as higher water absorp-
tion, more weakness in interfacial transition zone [19,20] would
degrade the mechanical properties of concrete containing recycled

https://doi.org/10.1016/j.conbuildmat.2018.08.147
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
1046 H. Yang et al. / Construction and Building Materials 188 (2018) 1045–1049

coarse aggregates compared with conventional concrete. This
paper aimed to study the mechanism of LP in MS on the hydration
products and microstructures that could further affect the com-
pressive strength of recycled aggregate concrete. X ray diffraction
(XRD) and Scanning electron microscope (SEM) tests were con-
ducted to investigate the hydration product and its microstructure
morphology separately.
2. Experiments
2.1. Raw materials and mix proportions
Demolished concrete from a highway pavement was crushed
and sieved as 5–31.5 mm coarse aggregate, with the physical prop-
erties listed in Table 1. The MS, bought from a local commercial
plant, was adopted as fine aggregate, which contains a high level
of LP due to the defect of crushing process. As LP improved the
compressive strength when its mass percentage in MS was lower
than 10–20% [6,12,14], here 15% mass percentage of LP was mixed
in MS in this investigation. The MS was first sieved using vibration
screening machine (ZBSX-92A) to achieve 0% mass percentage of
LP, and then 15% mass percentage of LP was mixed in MS. The min-
eral components of LP was determined using XRD test before con-
crete casting, with result showing that CaCO3, CaMg(CO3)2 and
little content of a-SiO2 were detected in these LP.
Two different mix proportions were determined in this paper
corresponding to two different kinds of MS (i.e. MS with 0% and
15% content of LP), the addition water (AW) was also added in this
mixture to consider the water absorption of RCA. Details were
shown in Table 2. For each mix, three cubic specimens with sides
of 150 mm were prepared for the compressive strength test, with
test results listed in Table 2. As can be seen in Table 2, 15% mass
percentage of LP in MS increased the compressive strength of con-
crete, a finding that agreed with the test result obtained by other
researchers [6,14].
2.2. XRD and SEM tests
The experimental investigation in this paper comprised of XRD
and SEM studies on the hydration product of cement paste and on
the microstructures of recycled coarse aggregate concrete
separately. Samples MRC-0 and MRC-15 cured for 3 days (d), 7 d,
14 d, 21 d and 28 d were pulverized and the hydration cement
pastes were selected. Each cement paste was first immersed in
absolute ethanol solution for 24 hrs in order to terminate the
hydration reaction and then was kept in an oven for 24 hrs at
105 ± 5 °C until it reached to a constant weight. The dried cement
pastes were grinded into powder and then were submitted to test
Table 1
Physical properties of recycled coarse aggregate.
Grain size/mm Absorption/% Crushing index/% Apparent density/kg/m3
5–31.5 4.25 15 2613
the diffraction pattern using an X-ray diffractometer. The measure-
ment conditions of XRD were a tube voltage of 30 kV and a tube
current of 20 mA. Scans were repeated continuously from 5° to
80° with 0.1°/s using Cu target.
The microstructure morphology of concrete cured for 28 d was
tested using SEM method. Regular pieces of 10-mm size were cut
ensuring it containing recycled coarse aggregate, old harden
cement paste, and new harden cement past. The samples were also
immersed in absolute ethanol solution for 24 hrs to stop the hydra-
tion reaction, and then were kept in an oven for 24 hrs at 105 ± 5 °C
to remove evaporable water. Finally the samples were mounted on
metal stubs, and were sputter-coated before subjecting to the elec-
tron beam from HitachiS-3400W Scanning Electron Microscope.
3. Results and discussion
3.1. XRD patterns and hydration analysis
The XRD patterns of samples MRC-0 and MRC-15 at age of 3 d, 7
d, 14 d, 21 d, and 28 d are shown in Figs. 1 and 2. As can be seen in
Figs. 1 and 2, the principal hydration products were Ca(OH)2,
ettringite (AFt), Ca4Al2O611H2O and so on, while the C3S2H8 can-
not be clearly observed because this hydrate varied over a wide
range and its semi-amorphous nature. The peak of hydration prod-
ucts in XRD pattern characterized the content of these constituents
during the chemical reaction process. As the curing period
increased, the chemical cement compound gradually reacted, and
hydration products be formed continuously. It can be obviously
observed from Figs. 1 and 2 that the characteristic peak of Ca
(OH)2 was obscurely found in XRD patterns of both MRC-0 and
MRC-15 samples in the early hydration period. This type of peak
was clearly observed at age of 14 d, 21 d and 28 d, indicating that
C3A and C4AF were the most reactive compounds in the early
A A--CaCO3
B--SiO2
C--Ca(OH)2
D--AFt
B E--Ca4Al2O6·11H2O
C E C A
D BA ED
A A AA
B 28d
21d
14d
7d
3d
10 20 30 40 50 60 70 80
2-theta-scale
Fig. 1. The XRD pattern of MRC-0.

Table 2
Mix proportions.

Series W/C Content/kg/m3 fcu/MPa

W AW C MS LP RCA
MRC-0 0.40 195 45 487.5 707.0 0 1060.5 44.33
MRC-15 0.40 195 45 487.5 601.0 106.0 1060.5 46.81

Note: W-water; C-cement; RCA-recycled coarse aggregate; fcu-compressive strength.

 H. Yang et al. / Construction and Building Materials 188 (2018) 1045–1049 1047

A A--CaCO3 A A--CaCO3
B--SiO 2 B--SiO2
C--Ca(OH) 2 C--Ca(OH)2
D--AFt D--AFt
B
E--Ca 4Al 2 O6·11H2O B
C E C
D A D A A A AA 28d C
C A
BA DA A AA
D MRC-15
21d
14d
MRC-0
7d
3d
10 20 30 40 50 60 70 80
10 20 30 40 50 60 70 80 2-theta-scale
2-theta-scale
Fig. 4. The XRD patterns for 28 d.
Fig. 2. The XRD pattern of MRC-15.
ing that incorporating with LP did not change the composition of
hydrations. In addition, C3S and C2S can also be found in XRD pat-
hydration reaction, whereas C3S and C2S reacted little in 3 d and tern at 3 d curing, while after 28 d curing, these two compounds
7 d hydration period. However, because C3A and C4AF account cannot be clearly observed in concrete. This is due to that the
for only about 18% of Portland cement, the effects of the chemical chemical reaction of C3S and C2S occurred at the mid- and late-
reaction for these two compounds on compressive strength of con- curing, and the reaction had been basically completed at 28 d age.
crete in this period were limited. While the peak of Ca(OH)2, AFt Comparing the 28 d-patterns of sample MRC-15 and sample
and Ca4Al2O611H2O in XRD pattern gradually raised with the reac- MRC-0 in Fig. 4, it is also can be observed that the area of charac-
tion undergoing, demonstrating that the hydration of compounds teristic peak of Ca(OH)2 for sample with 15% LP was larger than
C3S, C4AF and C2S were largely taken place in the mid- and late- that of MRC-0. The increase of Ca(OH)2 content indicates an accel-
reaction period. eration of calcium silica, this is mainly related to that the CaCO3 in
Comparing the peak value at 23° in Figs. 1 and 2, one found that LP react with calcium silica to form calcium carbonate hydrate
the content of Ca4Al2O611H2O in MRC-15 was slightly lower than [21].
that in MRC-0. The chemical reaction of active CaCO3 in limestone
with 3CaOAl2O36H2O may be responsible for this result, which
shown as following:

3CaCO3 þ 3CaO  Al2 O3  6H2 O þ 5H2 O

! 3CaO  Al2 O3  3CaCO3  11H2 O ð1Þ
The 3CaOAl2O33CaCO311H2O interlaced with other hydration
product and densified the concrete structure, increasing the com-
AFt
pressive strength.
Figs. 3 and 4 show the comparison of hydrations between C-S-H
MRC-0 and MRC-15 at ages of 3 d and 28 d separately. As can be
seen in Figs. 3 and 4, no new characteristic peak was found in Ca(OH) 2
the XRD pattern of MRC-15 comparing with that of MRC-0, indicat-

A
A--CaCO3 (a) Ettringite and calcium hydroxide
B--SiO 2
C--Ca(OH) 2
D--AFt
F--C3S
G--C2S
A
FGCA A AA
D C F B MRC-15

MRC-0

10 20 30 40 50 60 70 80
2-theta-scale (b) C-S-H
Fig. 3. The XRD patterns for 3 d. Fig. 5. Morphology of hydration production of MRC-15.
1048 H. Yang et al. / Construction and Building Materials 188 (2018) 1045–1049

3.2. SEM images and analysis

Fig. 5 presents the SEM images of MRC-15. The main hydration

production in MRC-15 were C-S-H gel, AFt, and Ca(OH)2, who had
interconnection structure, needlelike structure and plate structure
respectively (Fig. 5). These hydration products accumulated,
crossed and bonded with each other, and then filled into the pore
structure of the cement stone with the development of hydration
reaction, which strengthened the structure of cement stone and
increased its compressive strength. Fig. 6 compares the morphol-
ogy of hydration productions between MRC-0 and MRC-15, with
results affirming the difference in morphology of hydration prod-
ucts of MRC-0 and MRC-15. The surface of AFt and Ca(OH)2 of
MRC-15 was smooth but it covered with micro-particle in the sur-
face of AFt and Ca(OH)2 for MRC-0, indicating that the LP changed
the morphology of hydration products to some extent.
The microstructures of cement matrix and of interface between
RCA and new cement stone for MRC-15 are shown in Fig. 7(a) and
(a) Cement matrix
(b). As can be observed from Fig. 7 (a), a lot of block-shape LP can
be observed in MRC-15, indicating that most of LP was inactive,
and only a few CaCO3 in LP entered into the hydrating reaction.
Similar with conventional concrete, the interface between RCA
and new cement stone in MRC-15 was also weak (Fig. 7(b)). An
obvious interface transition zone (ITZ) and micro-crack between

(b) ITZ between RCA and new cement

Fig. 7. The cement matrix and ITZ between RCA and new cement.

RCA and new cement stone can be observed. A small quantity of

LP also filled into this micro-crack, densifying the ITZ between
RCA and new cement stone, thus increasing the compressive
strength of MRC-15. The strengthening effect agrees with the com-
pressive strength result in this paper and the conclusions by other
(a) MRC-0 researches [6,13,14].

LP

(b) MRC-15
Fig. 6. The effect of limestone powder on the hydration products patterns. Fig. 8. The hydration products around the limestone power.
 H. Yang et al. / Construction and Building Materials 188 (2018) 1045–1049
The hydration products around the LP in MRC-15 were also
scanned in this investigation using SEM, with an image showing
in Fig. 8. As can be seen in Fig. 8, some of LP filled into the hollow
of cement matrix, and the hydration products gradually formed
and subsided in the surface of LP. As crystal nuclei, LP increased
the precipitating action of hydrations. The pore of cement paste
hosted LP, in which some hydration products adhered and grew
on the LP surface. LP sets seeds for nucleating new hydration
products, which lead the deposit of other hydration products such
as C-S-H, calcium hydroxide and ettringite. The pores with hydra-
tion product nucleation are densified, so the concrete containing LP
improved. At the later stage of the hydration, some LP can even
reacted with the hydration product of hydrated calcium aluminate
to form calcium aluminate carbonate hydrates, the process that
further densified the paste and lifted its strength accordingly.
4. Conclusion
The influence of limestone poweder (LP) on the hydration prod-
ucts and the microstructure of concrete containing manufactured
sand (MS) and recycled aggregate concrete was studied using
XRD and SEM methods. It is found that most of fine limestone
aggregate does not participated in the hydration reaction, except
some LP reacts with ettringite and calcium silica, forming hydrated
calcium aluminate and calcium carbonate hydrate respectively.
The hydration products and some amount of inert LP fill the pore
of recycled aggregate concrete and the ITZ between RCA and new
cement, improving the strength of concrete. The addition of LP in
MS also changed the morphology of the hydration products. LP sets
seeds for nucleating new hydration products, where other hydra-
tion products such as C-S-H, calcium hydroxide and ettringite set-
tle, a process that densified the pore of recycled aggregate concrete
and lifted the concrete strength.
Conflict of interest
The authors declare that there have no conflicts of interest to
this work.
Acknowledgments
The authors would like to acknowledge the financial support
received from Natural Science Foundation of China (Nos.
51768004 and 51478126).
1049
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