Cement and Concrete Composites 77 (2017) 86e101

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Cement and Concrete Composites

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

Effect of cement substitution by limestone on the hydration and

microstructural development of ultra-high performance concrete
(UHPC)
Wei Huang a, b, *, Hadi Kazemi-Kamyab b, Wei Sun a, Karen Scrivener a, b
a
Jiangsu Key Laboratory of Construction Materials, School of Material Science and Engineering, Southeast University, Nanjing 211189, China
b
Laboratory of Construction Materials, Swiss Federal Institute of Technology (EPFL), Ecublens, 1015 Lausanne, Switzerland

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

Article history: The effect of limestone on the hydration and microstructural development of ultra high performance
Received 9 July 2015 concrete (UHPC) with different levels of replacement (34%, 54% and 74% by volume) was investigated. Up
Received in revised form to 54% replacement of cement by limestone the mixes showed better workability and higher compressive
13 November 2016
strength (170 MPa at 56 days for 54% addition) compared to a classical mix (155 MPa) with no limestone
Accepted 21 December 2016
Available online 29 December 2016
replacement. The kinetics of hydration were compared for different replacement levels using isothermal
calorimetry. The phase development was quantified by X-ray diffraction with Rietveld method combined
with thermal gravimetric analysis. The pore structure was examined by mercury intrusion porosimetry.
Keywords:
UHPC
The composition of hydration products was determined by scanning electron microscopy with energy
Hydration degree dispersive X-ray analysis. The results showed that the hydration degree of the cement is increased from
Limestone 39% for classical UHPC to 66% for the UHPC with 54% of limestone.
Microstructure © 2016 Elsevier Ltd. All rights reserved.
C-S-H
Porosity

1. Introduction hydration degree of cement is only 30e35% [8], which means a

Ultra-high performance concrete (UHPC) is an engineered
cementitious material which exhibits outstanding mechanical
properties and excellent durability. With the incorporation of a
sufficient amount of steel fibers (minimum of 3% by volume), strain
hardening (SH) ultra-high performance fiber reinforced concrete
(UHPFRCs) can be produced which show reasonable tensile
strengths and strain hardening (compressive strength > 150 MPa,
tensile strength > 8 MPa with 1.5‰ strain hardening) [1]. UHPFRC
offers the possibility of designing innovative structures [2,3] and in
recent years it has been demonstrated that UHPFRC can be used as a
rehabilitation material for existing structures [1,4]. However, use of
UHPFRC remains limited due to its high cost. The high cement
content (1100e1300 kg/m3) and silica fume (around 20e26%) im-
pacts the price and environmental footprint [5e7].
Due to the ultra-low water to binder ratio (0.14e0.19), the
* Corresponding author. Jiangsu Key Laboratory of Construction Materials, School
of Material Science and Engineering, Southeast University, Nanjing 211189, China.
E-mail address: hw20063481@163.com (W. Huang).
significant quantity of cement clinker remains unhydrated, acting
as an expensive filler in the binder system. Consequently there is
interest to replace part of the cement clinker, with supplementary
cementitious materials (SCMs) [9e12]. However, commonly used
SCMs such as fly ash and ground granulated blast furnace slag,
might not be locally available everywhere. In addition, the mate-
rials for UHPC should of consistent quality to ensure that the high
level of performance is maintained. Limestone is a common natural
mineral, which has been widely used in normal concrete [13e15].
Denarie et al. [16] investigated the influence of replacing 50% of the
cement with limestone (D50 ¼ 10.5 mm) on the mechanical and
durability performance of a SH-UHPFRC; the SH-UHPFRC with
limestone had comparable or better performance in the fresh state
than the classical SH-UHPFRC. From a 4 point flexural bending test,
it was seen that the tensile response of the two mixes were very
similar. The air permeability test which gives information about the
transport properties of the material were very similar
(0.005  1016 m2) which is 10 times smaller than a good concrete
(0.03  1016 m2). This limestone based formulation was used for
the rehabilitation of bridges [16]. Habert et al. [4] used the life cycle

http://dx.doi.org/10.1016/j.cemconcomp.2016.12.009
0958-9465/© 2016 Elsevier Ltd. All rights reserved.
 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101 87

Table 1 assessment method to compare different solutions for bridge

Physicochemical properties of the raw materials used. rehabilitation from an environmental point of view; the analysis
Oxide comp. (wt%) Cement Silica fume Limestone showed that rehabilitation with ECO-SH-UHPFRC which has 50% of
SiO2 22.44 97.92 0.07
limestone (D50 ¼ 8 mm) had a lower global warming potential than
Al2O3 2.76 0.00 0.00 the traditional solutions. Yu et al. [17] used the modified Andreasen
Fe2O3 2.24 0.05 0.02 & Andersen particle packing model to design UHPFRC with lime-
CaO 68.05 0.29 56.90 stone (D50 ¼ 10 mm); the results revealed that using fillers as a
MgO 0.91 0.15 0.13
cement replacement to design UHPC can improve its workability.
SO3 2.25 0.03 0.05
Na2O 0.19 0.22 0.07 However, the detailed microstructure and hydration kinetics of
K2O 0.11 0.31 0.00 UHPC with replacement of cement with limestone remains
TiO2 0.14 0.00 0.00 unreported.
P2O5 0.09 0.13 0.00
The aim of this paper is to look at different levels of replacement
Mn2O3 0.03 0.01 0.00
ZrO2 0.10 0.12 0.03
of the cement in UHPC with limestone in a systematic manner. The
Cr2O3 0.01 0.01 0.00 microstructural development of UHPCs was investigated by ana-
LOI(950 C) 1.28 0.77 42.73 lysing the time evolution of phases, pore structure and composition
C3S 62.35 of C-S-H. Furthermore, the relation between mechanical properties
C2S 20.28
and hydration degree was evaluated.
C3A 1.42
C4AF 5.83
CaCO3 0.98 97.61
Specific surface area m2/g (BET) 0.94 21.36 0.80 2. Materials and methods
Density (kg/l) 3.15 2.2 2.7
A sulphate resistant cement CEM I 52.5N, Betocarb HP-OG

Fig. 1. Particle size distribution of the raw materials measured by laser granulometry.

Table 2
Formulation of UHPC mixes and flow spread.

Mass (kg/m3) Volume (l/m3)

CSF CSFLS34 CSFLS54 CSFLS74 CSF CSFLS34 CSFLS54 CSFLS74

Cement 1251.2 825.8 575.6 325.3 397.2 262.2 182.7 103.3

Silica fume 291.3 192.3 134 75.7 132.4 87.4 60.9 34.4
Limestone / 486.2 772.2 1058.2 180.1 286.0 391.9
Superplasticizer(dry content) 28.2 10.5 5.1 5.2 27.3 10.2 4.9 5.04
Quartz sand 407.8 444.4 455.7 455.4 152.2 165.8 170.0 169.9
Water total 201.4 201.4 201.4 201.4 201.4 201.4 201.4 201.4
W/C 0.16 0.24 0.35 0.62
W/B 0.13 0.13 0.14 0.14
Spread (mm) 179 360 378 444
88 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101
limestone powder from Omya, undensified Elkem microsilica
Grade 971-U, and quartz sand were used in this study. Their
chemical compositions by X-ray fluorescence (XRF) and phase
composition by Rietveld refined XRD are shown in Table 1. The
Brunauer-Emmet-Teller (BET) specific surface area was determined
with a Micromeritics Gemin 2375 V4 instrument using nitrogen gas
at liquid nitrogen temperature; the results are shown in Table 1. The
particle size distributions, obtained using Malvern Mastersizer type
S laser beam granulometer, are shown in Fig. 1.
The UHPC formulations investigated are summarized in Table 2,
and the particle packing densities based on the compressive
packing model by De Larrard and Sedran [19] are shown in Fig. 2.
Fig. 2. Packing density of a ternary system of cement, silica fume and limestone
(Packing densities a of cement, silica fume and limestone are 0.538, 0.64, and 0.493
[18], compaction index was 9 [19]).
Fig. 3. Compressive strength development of UHPC mixes.
UHPC mixes were designed to have the same total binder volume
and water content. The volume ratio of silica fume to cement was
kept at 1:3. The volume of limestone in the binder system was: 0,
34%, 54% and 74%. The workability was adjusted using GLE-
NIUM®SKY 561 superplasticizer (25% solid content) from BASF.
Based on the mini cone test [16], the flow spread of UHPC mixtures
were determined, and are shown in Table 2.
It should be noted that the superplasticizer values shown in
Table 2 refer to the dry content, while the total water amount is the
sum of water in the superplasticizer and the water added sepa-
rately to the mixes. The value of sand content varied slightly due to
an error in the calculation, but this difference of around 10% is not
believed to have a significant impact on the mechanical properties.
Furthermore, the sand is inert and does not affect the microstruc-
tural development in the paste which concerns most of the results
presented here.
In this case, the use of a limestone with a fairly narrow particle
size distribution in the same range as the cement slightly decreases
the packing density as the amount of silica fume was less (Fig. 2),
nevertheless the workability was still dramatically improved for
the mixes with limestone, which allowed the amount of super-
plasticizer required to be reduced. Even though the amount of
superplasticizer was reduced to obtain reasonable mixes the flow
spread of the limestone mixes was still higher as indicated in
Table 2.
The mixing and casting of all the mixtures was done at 20  C. All
powders were mixed for 3 min with a speed of 61.5 rpm. Then the
water and superplasticizer were added while the mixer was
running until the powder changed into quasi-liquid state, the speed
was increased to 123 rpm for 2 min, followed by 1 min at 61.5 rpm.
The mortar samples were cast in 40  40  160 mm moulds and
then sealed cured. The paste samples were cast in plastic cylinder
moulds with 34 mm diameter and 50 mm height, and then sealed
cured; hydration of paste samples were stopped by immersing
3 mm thick slices in isopropanol for 7 days, and further vacuum
drying for at least 3 days before further preparation. The method of
arresting hydration by solution exchange via immersion in
 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101
Fig. 4. Heat evolution of UHPC with 4 levels of limestone replacement: a) Heat Flow (mW/g cement); b) Heat Flow (kW/m3 binder); c) Cumulative Heat (J/g cement); d) Cumulative Heat (kJ/m3 binder).

89
90 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101

isopropanol, and then vacuum drying has shown to have less

damaging effect on the microstructure; more information on
comparison of the various methods to stop hydration and method
used herein can be found in Refs. [20,21,22].
Compressive strength measurements were carried out on six
cube samples with 40 mm dimensions, cut from 40  40  160 mm
mortar prism samples at 1, 3, 7, 14, 28 and 56 days; the test was
conducted using a Walter þ Bai testing machine at a loading rate of
1.5 kN/s. Cut cubes were used rather than the normal method of
first testing the prisms in flexure and then making compressions
test on the broken ends as the brittle nature of the UHPC without
fibers lead to multiple fracture in flexure. The cutting with a dia-
mond saw lubricated with water did not significantly damage the
cubes.
Isothermal conduction calorimetry was carried out using a TAM
Air calorimeter (TA Instruments) at 20  C for 28 days. 10 g of paste
mixed at 20  C was inserted as quickly as possible into the ampoule
and placed in the calorimeter. More information about calorimetry
could be found in Refs. [23,24].
X-ray diffraction (XRD) measurements were carried out on fresh
slices before stopping hydration; the data were collected using a
Panalytical X'Pert Pro diffractometer (CuKa, l ¼ 1.54 Å) working in

Fig. 5. XRD profiles of UHPC with 4 levels of limestone replacement at 28 days.

Bragg-Brentano geometry under 40 mA and 45 kV operating con-
ditions. Samples were scanned on a rotating stage between 5  and
65  (2q) using an X'Celerator detector with a step size of
0.0167  (2q) and a time per step of 30 s. The XRD quantitifaction
was done by the means of Rietveld analysis, which is detailed in
Refs. [25,26].
Thermogravimetry analyses (TGA) were carried out with Met-
tler Toledo TGA/SDTA 851 balance. 50 mg of sample from dried
slices (after stopping hydration with isopropanol) was crushed into
a fine powder and heated at a constant rate of 10  C/min from 30  C
to 950  C in a 30 ml/min flow of nitrogen. Related information can
be found in Ref. [27].
Mercury intrusion porosimetry (MIP) was carried out on
Thermo Scientific Pascal 140 and 440 machines with a pressure
capacity of 400 MPa. Five pieces of samples, approximately 1.5 g,
were used for analysis. The parameters used were 0.48 N/m for
surface tension and 140  C for the mercury contact angle. More
information on proper use of MIP on cementitious materials and
the analysis of the data obtained can be found in Refs. [28,29].
For image analysis, the dried slices were impregnated using
epoxy resin (EPO-TEK®301) under vacuum and polished down to
1 mm using diamond sprays and with petrol as a lubricant. The
polished samples were examined by backscattered electron (BSE)
and energy dispersive X-ray analyses (EDS, Bruker AXS XFlash
Detector 4030) in a scanning electron microscope (SEM, FEI Quanta
200) with an accelerating voltage of 15 kV. The detailed informa-
tion about the SEM-BSE-EDS could be found in Ref. [30].

3. Results

3.1. Compressive strength

The compressive strength development of the UHPC mixes is

shown in Fig. 3. The CSFLS74 mix which has the highest amount of
limestone shows low strength values compared to the other mixes
during the entire hydration period. Because of the lower super-
plasticizer dosage in CSFLS34 and CSFLS54 they have less retarda-
tion compared to the CSF mix, and thus higher one day strengths.
The effect of retardation is gone by three days of age, after which
the strength development of these three blends is very similar.
Except for the CSFLS74 mix, the compressive strength of all the
UHPC mixes at 14 days reached approximately 150 MPa and sur-
passed this value under sealed conditions without any heat
 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101 91

Fig. 6. Differential thermal gravimetric curves of UHPC: a) Different replacements of limestone at 28 days; b) 54% of limestone at different ages; c) The first peak range.
92 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101

treatment. The strengths at 56 days for CSF, CSFLS34 and CSFLS54
were in the range 155e180 MPa.
3.2. Isothermal calorimetry
The hydration kinetics of UHPC were followed by isothermal
calorimetry. Fig. 4a and c show the heat release normalised per
gram of cement. It can be seen that the main hydration of all the
UHPC mixes occurs in the first 3 days. The hydration of the CSF mix
has a longer dormant period due to the higher amount of
superplasticizer which was needed to reach the minimum work-
ability. The cumulative heat per gram of cement increases with the
increasing replacement of limestone due to the dilution effect,
which provides more available water and space for the cement
hydration.
However, if the heat released is shown per unit volume of binder
(Fig. 4b and d), the UHPC mix CSFLS74 has the lowest total cumu-
lative heat while the other three mixes have comparable total cu-
mulative heat. These results show that extra reaction of the cement
clinker component compensates for the replacement of clinker by

Fig. 7. Water loss mainly from the decomposition of C-S-H.

Fig. 8. Evolution of calcium hydroxide content.

 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101
Fig. 9. Time dependent phase development for UHPC: a) CSF; b) CSFLS34; c) CSFLS54; d) CSFLS74. Error bars are not given for the sake of clarity. The apparent increase in the amount of CaCO3 seen gives an idea of the variations due to
error of measurement.

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W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101
Fig. 10. Evolution of hydration degree of cement: a) Determined by XRD with Rietveld analysis; b) Determined by image analysis.
 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101 95

limestone up to 54% replacement and is consistent with the of calcium hydroxide, 400  C-500  C; the third peak is the decar-
compressive strength development. bonation of calcium carbonate, 500  C-800  C [32]. As seen in
Fig. 6a, the peak of calcium carbonate becomes stronger and
broader with the increasing amount of limestone. However, the
3.3. X-ray diffraction and thermal gravimetric
peaks for a given mix remain constant at different ages (Fig. 6b),
which indicates that the limestone does not react significantly,
Fig. 5 shows the X-ray diffraction profiles of UHPC mixes with
consistent with the XRD results. When the first peak is enlarged
different levels of limestone at 28 days. The main phases seen are
(Fig. 6c) a broadening on the high temperature side in the range
the clinker phases and calcite. Low amounts of portlandite (due to
130e160  C may indicate a small amount of ill crystallised AFm
the pozzolanic reaction of silica fume) and ettringite are also seen.
phases.
As the limestone replacement increases, the peak of calcite be-
The amount of water loss up to 400  C normalized per gram of
comes more pronounced. No AFm phases (calcium mono-
cement was measured from the TGA results. This comes mainly
sulfoaluminate 9.75  , calcium hemicarboaluminate 10.75  and
from the decomposition of the C-S-H plus the small amounts of
calcium monocarboaluminate 11.5  [13,31]) can be seen in the XRD
ettringite and AFm phases. Fig. 7 shows the evolution of this water
profiles. This may be attributed to the low C3A content of the
loss. It is seen that increasing the limestone replacement increases
cement used, the fact that AFm phases generally have low crys-
the amount of C-S-H formed per unit weight of cement. This
tallinity and the dilution effect of limestone at the higher addition
observation is in agreement with the result of isothermal calo-
levels. The peaks of ettringite and ferrite are less distinct as the
rimetry test, since the main heat evolution comes from the cement
amount of limestone increases, due to dilution.
hydration which reacts with water to generate C-S-H and
Fig. 6 shows the differential thermal gravimetric (DTG) curves of
portlandite.
UHPC mixes. There are three major peaks on the curves: the first
The evolution of portlandite in the mixes normalized per gram
peak is associated with the dehydration of C-S-H, ettringite and
of cement is presented in Fig. 8, which is determined from XRD and
AFm phases, up to 400  C; the second peak is the dehydroxylation

Fig. 11. SEM-BSE images of UHPC matrixes with different replacements of limestone at 28 days:a) CSF; b) CSFLS34; c) CSFLS54; d) CSFLS74.
96 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101

Fig. 12. SEM-BSE images of inner product around cement grains and outer product away from cement grains (From top to bottom: CSF, CSFLS34, CSFLS54 and CSFLS74).
 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101
TGA. At early ages, the amount of portlandite increases relative to
the amount of cement present, consistent with the enhancement of
the cement reaction by dilution discussed above. After approxi-
mately four days, the content of calcium hydroxide for all mixes
starts decreasing due to the pozzolanic reaction of portlandite with
the silica fume. Since the amount of silica fume relative to cement is
constant, it is clear that the dilution with limestone also increases
the reaction of the silica fume.
Fig. 9 shows the time dependent phase development for all the
main phases (C3S, C2S, C3A, C4AF, Ca(OH)2, ettringite, CaCO3,
amorphous phase (mainly silica fume and C-S-H) and the free
water). The quantifications of crystalline phases were carried out by
XRD with Rietveld analysis. The “unreacted” water was calculated
by subtracting the total added water from the bound water, up to
around 500  C, this water will mainly be present in the gel pores of
the C-S-H. There is still a significant amount of unhydrated cement
in the CSF mix due to insufficient water and or space. However with
increasing limestone replacement, the amount of unhydrated
cement decreased. All the mixes react rapidly in the first 7 days, and
thereafter very slowly.
The hydration degree of cement was determined by the Rietveld
analysis, using EQ. 1, and by image analysis. More detailed infor-
mation could be found in Refs. [25,26] about Rietveld analysis, and
[30,33] on image analysis.
ðC3 S þ C2 S þ C3 A þ C4 AFÞðtÞ
DoHðtÞ ¼ 1 
ðC3 S þ C2 S þ C3 A þ C4 AFÞðt ¼ 0Þ
The overall degree of hydration of cement (DoH) was measured
by XRD with Rietveld analysis and by image analysis on BSE images
at 28 days. Fig. 10a shows the hydration degree of cement as a
function of time for all the mixes by XRD, while Fig. 10b shows that
the degree of hydration evaluated by the two methods agree well.
From Fig. 10a it is clear that the hydration degree increased rapidly
in the first 7 days and slowed down significantly thereafter. At the
age of 56 days, the hydration degrees of cement with 0, 34%, 54%
and 74% of limestone by volume were 39.0%, 54.2%, 66.2% and 79.8%
respectively. Note that degree of hydration of mix CSF.LS74 reached
only 79.8% although the W/C was 0.62. The degree of hydration of
C3S, C2S, and Ferrite at 56 days in mix CSF.LS74 was 90%, 52.1% and
90.2%. The lower degree of reaction of C2S decreased the overall
degree of hydration of the cement. The degree of hydration of the
Fig. 13. SEM-BSE images of outer product away from cement grains in mix CSFLS54: a) 1 d; b) 28 d.
97
cement phases is very sensitive to the relative humidity develop-
ment. It has been shown that the degree of hydration of C2S
significantly decreases as the relative humidity decreases to 90%
[34] and alite stops hydrating under 80% relative humidity [35].
3.4. Electron microscopy results
Fig. 11 shows the SEM-BSE images of the UHPC matrices with
different limestone replacements at 28 days of hydration. In the
images in Fig. 11, the brighter areas are associated with anhydrous
cement clinker, limestone are a uniform grey, while the hydration
products with interspersed silica fume have a similar grey level
between the particles. The black zones are the voids filled with
resin. In all mixes, except some minor entrapped air, the matrices of
UHPCs are very dense. It can be seen that higher is the amount of
limestone in the mixes, the lower is the amount of unhydrated
cement. However even in the case of CSFLS74, which has the lowest
cement content, there is still some unhydrated cement remaining.
Fig. 12 shows the SEM-BSE images of the inner product around
cement grains (left) and outer product away from the cement
grains, and around the limestone grains (right). It is clear that the
rim of inner C-S-H for classical UHPC is very thin since the degree of
hydration is very low. With increasing amounts of limestone, the
rim of inner C-S-H becomes more pronounced, which is consistent
with the increase in degree of hydration (Fig. 10). In the regions
(1) away from the cement grains, the product is a mix of outer C-S-H
and silica fume in the reference sample. Since there are no lime-
stone particles in classical UHPC, the materials between the cement
grains consists of outer C-S-H intermixed with silica fume. For the
mixes with limestone replacement, the limestone particles are also
surrounded by outer product C-S-H; this shows that the hydration
products have been deposited homogenously everywhere. This is
facilitated by the fact the nucleation of C-S-H is favoured on the
surface of limestone particles as shown by Berodier and Scrivener
[36].
Fig. 13 shows the SEM-BSE images of region away from cement
grains in the mix CSFLS54 at 1st day and 28 days. It is clear that no
significant difference can be found between them which shows the
dense structure of UHPC is already formed from early stages of
hydration due to the well selected particle packing, and sufficient
amount of paste.
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W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101
Fig. 14. Chemical composition of inner C-S-H of UHPC mix at 28 days: a) Cloud points; b) Average Ca/Si ratio versus W/C.
 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101
Fig. 15. Comparison of pore structures of UHPC with various levels of limestone replacement and plain Portland cement paste at 28 days: a) Cumulative pore volume; b) Pore size distribution.

99
Fig. 16. Pore size distributions of UHPC mixes at different ages: a) Mix CSF; b) Mix CSFLS54.
100 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101

Table 3 been shown in Fig. 16a, and for the CSFLS54 mix in Fig. 16b,
Critical pore radius of UHPC mixes at different ages (nm). respectively. Table 3 and Table 4 compare the critical pore radius
1d 2d 3d 7d 14d 21d 28d 56d and total porosity for these mixes, respectively. As the hydration
CSF 22.2 8.5 7.0 5.5 4.0 3.4 3.2 3.1
takes place, the mix CSFLS54 undergoes significantly different pore
CSFLS54 14.3 13.3 10.4 7.4 6.3 5.3 4.4 2.0 structure development compared to CSF. Since the amount of
superplasticizer in CSFLS54 was lower compared to CSF, the hy-
dration started earlier (Fig. 16a and b), and at 1 day there is more
Table 4 hydration products formed, filling the space. That is why CSFLS54
Total porosity of UHPC mixes at different ages (%). has smaller critical pore radius at 1 day compared to CSF. As hy-
1d 2d 3d 7d 14d 21d 28d 56d
dration takes place, the critical pore radius in both mixes shifts to
smaller pore size range, and the magnitude of the peak, decreases.
CSF 23.5 15.1 13.6 10.7 9.0 8.1 7.7 6.6
In the case of the CSF mix the magnitude of the critical pore radius
CSFLS54 15.9 13.0 14.3 12.6 11.6 10.8 11.0 7.0
decreases significantly as function of hydration time (Table 3); but
levels off from 14 days forward at about 2e4 nm. In case of the
CSFLS54, the magnitude of the critical pore radius continues to
The composition of inner C-S-H was determined from numerous
decrease up to 28 days reaching around 4e5 nm. At long term the
EDS analyses (Fig. 14) in the inner product regions. Analyses could
values of the critical pore radius and total porosity are fairly similar
not be made in the outer product regions due to the presence of
in these systems (Tables 3 and 4).
silica fume and limestone. More than 35 different images
with  10000 magnification were analysed; Two to three points
were chosen manually on each selected image in a manner to avoid, 4. Discussion and conclusion
as far as possible, the surrounding phases. However, due to the very
thin thickness of inner C-S-H in the CSF mix (Fig. 12) (<interaction From our studies, it was concluded that replacement of cement
volume of about 1e2 mm at 15 kV), the cloud of points are scattered with limestone is beneficial in UHPC mixes both from the
significantly, and the average ratio of Si/Ca for CSF could not be perspective of mechanical properties and from the perspective on
estimated accurately for this mix. The average values of Ca/Si of the the hydration and microstructural development. Our results show
inner CSH for CSFLS34, CSFLS54 and CSFLS74 are 2.01, 1.86 and 1.73; that adding limestone in UHPC can promote the cement hydration
this ratio decreases as the limestone replacing the cement increases (Fig. 4c), and the hydration degree can be increased from 39% for
in the mixes. Note that the water-to-cement ratio also increases classical UHPC to 66% for CSFLS54 (Fig. 10). The limestone in this
with the increasing limestone amount; the relationship between study did not react significantly (due to the low C3A content of the
Ca/Si ratio and W/C is in good agreement with the results of Bazzoni cement), but did contribute to the good distribution of hydrates
for pure C3S paste with different W/C ratios [37]. throughout space by facilitating the nucleation and growth of outer
C-S-H.
The traditional method of designing a UHPC mix is to optimize
3.5. Pore structure analysis by MIP the packing of the granular ingredients [17,19,40,41]. It was seen
that by increasing the limestone replacement, the packing density
The pore structures of UHPC mixes with various levels of lime- of the mixture is partially reduced; but this reduction seems not to
stone replacement were compared at 28 days (Fig. 15); In addition, affect the compressive strength development and magnitude up to
the 28 days pore structure of plain Portland cement paste with W/ 54%.
C ¼ 0.4 reported by Berodier and Scrivener [38] is also shown. It is The mix with 74% replacement of cement with limestone had
clear that the porosity of UHPC mixes increases as the limestone significantly lower compressive strength values. This reduction can
replacing the cement increases (Fig. 15a). However, up to 54% be attributed simply to the fact that the amount of reactive phases
limestone, the porosity is lower than the normal cement paste. The (cement and silica fume) is insufficient to give enough hydrates to
threshold pore radius, which is defined as the radius when the fill as much of the empty space as in the other mixtures. In the other
mercury starts to penetrate the sample [39], is approximately mixtures the degree of reaction is effectively limited by the space
comparable in the various UHPC mixes, and also the normal cement available.
paste (Fig. 15a). However, if we consider the critical pore radius (the Finally the effects of cement replacement by limestone, on the
inflection point on the cumulative pore volume curve, and the price and the CO2 emission of UHPC were estimated and summa-
maximum peak on the pore entry size distribution curve) (Fig. 15b), rized in Table 5; it should be noted that the limestone used in this
it is seen that classical UHPC has finer pore size range compared to investigation was quite expensive as it had a controlled particle size
limestone UHPC mixes, and the normal cement paste. It can be seen distribution as this is easier to use in laboratory studies. However
that the critical pore radius increases as the limestone replacement the unit bulk price of limestone is normally much lower than this
increases; however even CSFLS74_28d mix has smaller critical pore kind of special product. Taking a more typical price for limestone, it
radius than the normal cement paste. can be seen that by replacing limestone with the cement, the total
Evolution of the pore structure over time for the CSF mix has price and CO2 emission in cubic meter of UHPC decreases

Table 5
Evaluation of price and CO2 emission of UHPC mixtures in this investigation.

Component Unit price CO2 Emission (kg/kg) [4] Mixes Price CO2 Emission
(CHF/kg) (CHF/m3) (kg/m3)

Cement 0.35 0.84 CSF 1900 1137

Silica fume 3.30 0.00031 CSFLS34 1276 739
Limestone 0.10 0.026 CSFLS54 964 520
Superplasticizer 3.00 0.75 CSFLS74 714 317
Quartz sand 0.40 0.0024
 W. Huang et al. / Cement and Concrete Composites 77 (2017) 86e101 101

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