Construction and Building Materials 256 (2020) 119454

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Construction and Building Materials

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Hydration and mechanical properties of UHPC matrix containing

limestone and different levels of metakaolin
Zongyun Mo a, Rui Wang b, Xiaojian Gao a,⇑
a
School of Civil Engineering, Harbin Institute of Technology, Harbin 150090, China
b
The Key Laboratory of Urban Security and Disaster Engineering, MOE, Beijing University of Technology, 100124, China

h i g h l i g h t s

Addition of 15% MK induced the best mechanical strength for UHPC mortar.

MK accelerated the hydration heat evolution of UHPC paste after 24 h.

Addition of over 10% MK significantly refined pore structure of UHPC paste.

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

Article history: In this paper, the hydration process and mechanical properties of UHPC matrix incorporated with lime-
Received 4 August 2019 stone (LS) and different substitution rates of metakaolin (MK) were investigated. MK was added with five
Received in revised form 30 April 2020 levels of substitution (0, 5%, 10%, 15% and 20%) and LS was kept at 30% of the total binder mass.
Accepted 3 May 2020
Mechanical properties, hydration heat, hydration products and pore structure measurements were car-
Available online 13 May 2020
ried out for every mixture. The results show that the hydration rate as well as the hydration heat peak
of UHPC pastes decrease with MK level in the first 24 h possibly due to the higher superplasticizer usage,
Keywords:
but the hydration process is accelerated with the incorporation of MK after 24 h. The pozzolanic reaction
UHPC
Metakaolin
of MK and synergistic effect with LS consumes portlandite and induces the formation of more CSH gels
Limestone filler with the improved microstructure of UHPC matrix. The trace of calcium monocarboaluminate (Mc) phase
Hydration process can be observed in UHPC paste samples with a low MK substitution (5%), and becomes weaker with the
Mechanical strength higher MK dosage. The pozzolanic reaction of MK with replacement level of 15% results in the best long-
term compressive strength of UHPC mortars. Therefore, the incorporation of both MK and LS at an opti-
mal level is favorable to manufacture UHPC with improved mechanical properties.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction reveals a specific superiority in the fields of rehabilitation engineer-

In recent years, ultra-high performance concrete (UHPC) has
been extensively investigated and manufactured worldwide
because its mechanical and durability properties are substantially
superior to normal and high performance concretes. [1–2]. In many
literatures, UHPC is defined as a fiber-reinforced cement-based
material with compressive strength of as high as 150 MPa [3–5].
According to Chinese standard, the concrete possessing a compres-
sive strength of over 100 MPa also can be defined as UHPC [6]. In
recent years, significant efforts have been put into the formulation
design [7], preparation process [8] and mechanical performance
enhancement [9] of UHPC. In terms of practical application, UHPC
⇑ Corresponding author.
E-mail address: gaoxj@hit.edu.cn (X. Gao).
ing, long-span bridges and precast concrete components [10–12].
As is well known, the use of supplementary cementitious mate-
rials (SCMs) is an efficient approach in reducing the clinker usage
and improving mechanical and durability properties of cementi-
tious materials [13–18]. It is acknowledged that the outstanding
properties of UHPC result from the mixing proportion optimization
on the basis of the maximum packing density theory [19]. UHPC is
normally manufactured employing a low water to binder ratio
(w/b) from 0.14 to 0.24, a high dosage of cementitious materials
(around 1100–1300 kg/m3) as well as pozzolanic powders such
as silica fume (200–350 kg/m3) [17]. It was reported that the
cement hydration degree in UHPC materials is merely up to
30–35%, implying that most of unhydrated cement and silica fume
grains only act as physical fillers [20–22]. Subsequently, UHPC
costs higher than ordinary concretes and the actual application of

https://doi.org/10.1016/j.conbuildmat.2020.119454
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 Z. Mo et al. / Construction and Building Materials 256 (2020) 119454
UHPC is thus limited in some regions. Besides, the extensive uti-
lization of Portland cement in UHPC also induces significant carbon
footprints [23]. Therefore, it is of particular importance to investi-
gate novel eco-UHPC with less energy consumption and lower cost.
Supplementary cementitious material has been considered as a
reasonable method to reduce such environmental impacts.
In recent decades, limestone (LS) powder has been popularly
used in cement-based materials for its low cost and high availabil-
ity [24,25]. Proper proportioning of LS can improve microstruc-
tural and mechanical properties of UHPC due to its filler effect,
nucleation effect, dilution effect and chemical effect [21,26]. For
instance, higher compressive strength after 28 days can be
obtained in UHPC replacing 54% cement with LS by volume com-
pared to that of the reference without LS replacement [21].
Besides, metakaolin (MK) can be used to replace silica fume (SF)
in UHPC due to similar pozzolanic activity [27,28]. Owing to the
outstanding reactivity of MK in cement-based materials, the appli-
cation of MK has attracted extensive attention in these years [29].
MK can be obtained by calcining clay with a minimum kaolinite
content of 85% at around 800 °C [30,31]. Regarding the application
of MK to UHPC, it was reported that the addition of 20% MK to
replace SF showed a comparable strength for UHPC with room
temperature curing condition and a higher strength after exposure
to a steam curing regime [27,28]. However, MK with high specific
area maybe degrade the fluidity of cementitious materials due to
its higher water requirement and irregular particle shape when
compared with silica fume.
Recently, calcined clay with lower kaolinite content than MK
has been extensively researched on its potential application to
cement based materials [32]. Among which, the combination of
calcined clay with low kaolinite content and limestone (LS) into
cementitious materials, being called LC3 system, has been
regarded as an efficient solution on significantly reducing envi-
ronment footprint and also decreasing cost of cement in concrete
[33–35]. It is demonstrated that the existence of aluminum phase
in calcined clays leads to a synergistic effect with limestone (LS)
for generating carboaluminates phase [33]. Therefore, it is favor-
able for reducing the cement usage in concrete without signifi-
cant sacrifice of strength. Based on Avet’s study [36], the
calcined clays with lower kaolinite content than MK, in LC3 sys-
tems have shown similar synergistic and pore size refinement
effect on 28 days cement paste with MK. For normal concretes
with w/b of higher than 0.3, the combination of calcined clay
and LS to partially replace cement can reduce the material cost
and environmental impacts without visible sacrifice of mechani-
cal properties [36,37]. The incorporation of calcined clay and LS
in UHPC mixtures to form a ternary cementitious system with
very low w/b ratios was also reported by Huang [38]. It is indi-
cated that the combination of calcined clay with moderate LS
replacement presented equivalent compressive strength and
microstructure for UHPC when compared with the silica fume
added mixture.
Although previous studies have demonstrated that MK can
replace SF to manufacture UHPC without impairing the mechani-
cal properties, the combination effects of variable dosages of MK
and limestone on the hydration and microstructural development
of UHPC has not been fully investigated. Therefore, the objective
of this research is to gain insights into the hydration and mechan-
ical properties of UHPC matrix prepared by different replacement
levels of MK and a constant dosage of LS (30%) with curing ages.
Five replacement levels of MK (0, 5, 10, 15 and 20%) were
adopted to prepare UHPC mortar and paste mixtures with a low
w/b of 0.20. Mechanical properties, hydration heat, phase compo-
sition and pore structure measurements were carried out for
these mixtures.
2. Experimental
2.1. Raw materials and mix proportions
The used Portland cement (PC) was produced by China United
Cement Corporation, being accordance with P.I 42.5 as required
by Chinese Standard GB175-2007 [39] and with a Blaine fineness
value of 342 m2/kg. MK with over 90% kaolinite content and LS
were produced by Lv Huan Processing Plant of Minerals (Lingshou
County, China) with specific surface areas of 25 000 m2/kg and
913 m2/kg, respectively. Fine quartz sand (S) with the maximum
particle diameter of 0.95 mm was supplied by Sinomo Factory
(Xiamen, China). A polycarboxylate-based superplasticizer (SP)
was adopted to improve the flowability of fresh paste and mortar
mixtures [40]. It is a white powder in solid state with a water
reduction range of 25–45%. Chemical compositions and particle
size distributions of raw materials are summarized in Table 1
and Fig. 1, respectively.
In this study, cement paste and mortar mixtures with labels of
PLS and CLS were designed to simulate UHPC matrix. Mortar mix-
tures were prepared to determine the compressive and flexural
strength while paste mixtures were used to investigate the hydra-
tion mechanism and microstructure. Table 2 presented the mix
proportions of mortar specimens while paste samples were
obtained from the corresponding mortar mixtures by getting rid
of sand aggregates. The water to binder ratio (w/b) was kept at
0.2 for all mixtures and the sand to binder ratio of mortars were
kept at 1.0. As shown in Table 2, LS was added at 30% of the total
weight of binder and MK was incorporated with levels of 0, 5%,
10%, 15% and 20% of the total weight of binder.
2.2. Mixing procedures, fresh properties and specimen preparation
Compared with ordinary concrete, the quality of UHPC mixture
is more sensitive to the preparation process and environment [41].
To minimize the impact of mixing operation, all pastes and mortars
were prepared by a planetary mixer with the same procedure.
First, all dry ingredients in the mixture were firstly mixed at a
low speed of 62 rpm for 2 min. Then the water containing dis-
solved superplasticizer was poured into the mixing pot and mixed
at the same speed for another 3 min. Finally, another 5 min mixing
was performed at a high speed of 125 rpm until a homogeneous
fresh mixture was obtained.
The fresh properties of mortar mixture including slump flow
and air content were measured. The slump flow were measured
on the basis of the test method for fluidity of cement mortar com-
plying with Chinese standard GB/T 2419-2005 [42]. The fresh mix-
ture was filled into the mini slump cone with upper inner
diameter, lower inner diameter and height of 70, 100 and
60 mm, respectively. Then the mini slump cone was removed ver-
tically and the flow table is dropped 25 times in around 25 s.
Finally two diameters, perpendicular to each other, were measured
and the mean value was calculated as the slump flow of UHPC mix-
ture as presented in Table 2. Additionally, the dosage of SP was
adjusted to guarantee a slump flow varied from around 240 to
300 mm for every mixture as shown in Table 2.
The air content of fresh mortar mixture was measured using the
water column method according to British standard EN 12350-7
[43] and the test results are reported in Table 2.
After the completion of mixing, the paste and mortar mixtures
were cast into prismatic molds with sizes of 40  40  160 mm3.
When the consolidation was completed, specimens with molds
were kept at a curing room with temperature of 20 ± 1 °C and rel-
ative humidity of 95 ± 5% in the first 24 h. Subsequently, all
 Z. Mo et al. / Construction and Building Materials 256 (2020) 119454 3

Table 1
Chemical compositions of cementitious materials (%).

Oxide SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O LOI C3S C2S C3A C4AF
Cement 22.88 3.47 2.48 64.75 2.36 2.44 0.51 / 1.24 56.54 20.87 6.22 10.31
MK 52.96 43.05 0.66 0.41 / 0.49 / 0.15 1.03 / / / /
LS 0.45 0.61 0.19 55.36 0.48 0.012 0.025 0.033 42.84 / / / /

as CBW and ABW, respectively, which can be calculated by the fol-

lowing formulas.
m1  m2 LB2
CBW ¼  ð1Þ
m4 1  LB4

m2  m3 LB3  LB2
ABW ¼  ð2Þ
m4 1  LB4

LB2 ¼ LCement2  ð0:7  wMK Þ þ LMK2  wMK þ 0:3LLS2 ð3Þ

LB3 ¼ LCement3  ð0:7  wMK Þ þ LMK3  wMK þ 0:3LLS3 ð4Þ

LB4 ¼ LCement4  ð0:7  wMK Þ þ LMK4  wMK þ 0:3LLS4 ð5Þ

Fig. 1. Particle size distribution of raw materials.
specimens were demolded and then submerged in water with tem-
perature of 20 °C up to the date of testing.
2.3. Hydration process of paste sample
Isothermal conduction calorimetry test was performed using a
TAM Air calorimeter (TAM Air 8-channel, TA 5 Instruments Inc.,
New Castle, USA) to trace the heating evolution of cement pastes
in the first 72 h. Around 10 g of paste mixture mixed at 20 ℃
was filled as quickly as possible into the ampoule with sealed
cap and put in the calorimeter. More information about the
calorimetry test can be found in Ref. [44].
High temperature calcination test was used to obtain the chem-
ically bound water for every paste mixture at various ages (1, 2, 3,
7, 14, 28 and 56 d). As is well known, the dehydration tempera-
tures of gel products (such as C-S-H and C-A-S-H) are below
400 °C and Ca(OH)2 can be fully dehydrated under 450 ~ 600 °C,
while the carbonate phases such as LS in paste samples will not
be decomposed until 680 °C [26]. The measurement accuracy of
mass was stipulated as 0.1 mg. About 1 g sample in a total 10 ml
crucible was calcined by an electric furnace with a heating rate
of 5 °C/min and maintained at 400 °C or 600 °C or 950 °C for 3 h.
Finally the calcined sample was slowly cooled to room tempera-
ture in the furnace. The bound water masses (dehydrated mass)
in the temperature ranges of ~400 °C and 400–600 °C were labeled
where CBW and ABW are the mass loss percentages at temperature
of ~400 °C and temperatures of 400–600 °C, respectively. m1
denotes the initial mass of sample after 3 days drying treatment
at 60 °C (g), as well as m2, m3 and m4 are the residual masses of sam-
ples after being heated to 400, 600 and 950 °C (g), respectively. LB2,
LCement2, LMK2 and LLS2 are the mass loss fractions of the unhydrated
ternary binder, cement, MK and LS at 400 °C, respectively. LB3,
LCement3, LMK3 and LLS3 are the mass loss fractions of the unhydrated
ternary binder, cement, MK and LS at 600 ℃, respectively. LB4,
LCement4, LMK4 and LLS4 are the loss on ignition of the unhydrated
ternary binder, cement, MK and LS, respectively. The loss on ignition
of water reducer is negligible due to few mass fraction. wMK is the
incorporation percentage of MK in paste.
Selective dissolution method of hydrochloric acid was
employed to determine the reaction degree of MK in paste samples
at different ages (1, 2, 3, 7, 14, 28 and 56 d). The reaction degree of
MK can be obtained from Eq. (6) on the basis of literature [45].
wMK  ½wHCl =ð1  wne Þ  ð1  wMK Þ  wCLS:HCL =wMK:HCL
w0MK ¼ ð6Þ
wMK
m1  m4 LB4
wne ¼  ð7Þ
m4 1  LB4
where w0 MK is the MK reaction degree, which is normalized to the
reacted mass of 1 g MK. wHCl is the residual mass fraction of paste
sample after dissolution in acid solution, while wCLS.HCL and wMK.
HCL are the residual mass fractions of LS-cement paste and MK in
acid solution, respectively. wne is the chemically bound water mass
of paste sample under the calcination at 950 °C. It is noted that the
measurement for every mixture were tested three times and the
average value was determined as the reaction degree of MK.
Differential Thermal Analysis (DTA) test was carried out by
TG/DTA Instrument (HENVEN Factory, Beijing). The dry paste

Table 2
Mix proportions for UHPC mortars.

Number Mix proportions (kg/m3/%) w/b w/c Flow spread (mm) Air content (%)
PC MK LS S SP
CLS00 774.8/70 0/0 332/30 1106.8/100 4.98/0.45 0.20 0.29 296 7.89
CLS05 719.4/65 55.3/5 332/30 1106.8/100 5.53/0.5 0.20 0.31 287 7.57
CLS10 664.1/60 110.7/10 332/30 1106.8/100 7.75/0.7 0.20 0.33 274 7.42
CLS15 608.7/55 166/15 332/30 1106.8/100 11.07/1.0 0.20 0.36 267 7.30
CLS20 553.4/50 221.4/20 332/30 1106.8/100 27.67/2.5 0.20 0.40 248 7.67
4 Z. Mo et al. / Construction and Building Materials 256 (2020) 119454
samples were heated from room temperature to 1000 °C with a
constant heating rate of 10 °C/min under nitrogen atmosphere.
The nitrogen flow was kept at 40 ml/min.
X-ray diffraction (XRD) measurements were carried out on
selected paste samples using a diffract meter (CuKa, k = 1.54 Å)
under 35 mA and 40 kV. Diffraction patterns were acquired
between 5° and 65° of 2h value with a step width of 0.02°. The
quantities of ettringite and AFm-CO3 by cement mass as well as
cement hydration degree were determined by carrying out Quanti-
tative Rietveld analysis with the external standard method, which
is elaborated in literatures [46,47].
Mercury intrusion porosimetry (MIP) test was conducted with a
maximum pressure capacity of 400 MPa, contact angle of 130° and
surface tension of 485 dynes/cm, respectively. The samples for MIP
test were selected from the inner part of cement specimens and cut
into around 30 pieces of cubic particles with sizes of about 3 mm.
It is noted that the hydration of cement paste samples for bound
water, MK reaction degree, DTA, XRD and MIP measurements were
stopped at designated ages. Particles with sizes of around 3 mm cut
from the prism specimen were placed in a cylindrical plastic bottle
with a diameter of 80 mm and height of 60 mm. Then these bottles
were filled by ethanol and sealed continuously for seven days.
Finally, these samples were dried in a vacuum oven at 60 °C for
48 h for excluding residual ethanol.
2.4. Mechanical strength measurement
Compressive and flexural strength of UHPC mortar specimens
were determined at 1, 2, 3, 7, 14, 28 and 56 d under a loading rate
of 2.4 kN/s complied with Chinese Standard GB/T 17671-1999 [48].
The flexural strength was measured with a three-point bending
test. Three specimens from the same batch were conducted with
the bending test. The final flexural strength was determined by
the average value of three measured results. The compressive
strength test was conducted on the basis of six broken specimens
from the flexural strength test. The average value of six testing
results was obtained as the final compressive strength for each
batch.
3. Results and discussion
3.1. Mechanical strength
Fig. 2 presents the mechanical properties of mortar specimens
with different curing ages. It should be mentioned that the com-
pressive strength for every mixture is not as high as those reported
for UHPC specimens (120 MPa or higher) [49]. This is because that
(a) Compressive strength
Fig. 2. Mechanical strength variation of mortar specimens with curing ages.
steel fibers were removed from the mixtures and the influence of
MK on UHPC matrix was mainly focused in this study.
It can be seen that the compressive strength for every mixture
increases with the longer curing age as expected. The growth
ranges of compressive strength are very rapid during the first
7 days and then tends slower for all UHPC mortars, being similar
to that of UHPC containing steel fibers [1]. At 1 day, the compres-
sive strength of MK contained mortars are lower than that of the
reference without MK. After 3 days, the compressive strength of
mortars blended with MK (except for CLS20) increase rapidly and
exceed that of the reference mix at 7 days. The compressive
strength of mortar mixtures blended with MK behaves a more out-
standing long-term increasing tendency, which is ascribed to the
synergistic effect of cement, MK and LS after 7 days [38,50,51].
Whereas the addition of 20% MK into mortar presents a lower com-
pressive strength than the control specimen before 7 days, being
attributed to the lower cement reaction rate caused by the higher
dosage of superplasticizer [28]. It is worth noting that CLS15 has
the highest strength in this study at 56 days. It reaches 66 MPa
at 3 days and 104 MPa at 56 days, being 8% and 32% respectively
higher than that of the control mixture without MK.
According to Fig. 2(b), the flexural strength for every mixture
presents a similar increasing trend with age to that of compressive
strength during the first 7 days. At 7 days, CLS05, CLS10 and CLS15
present flexural strength of 18.16, 17.51 MPa and 20.09 MPa,
respectively, being 134%, 129% and 148% of that of the control mix-
ture (13.59 MPa). But the dosage of 20% MK leads to a 10% reduc-
tion of flexural strength compared with the control mixture. When
the curing age is longer than 14 days, most of mixtures (except for
CLS20) present a decreasing tendency of flexural strength with
ages. This phenomenon may be possibly attributed to the forma-
tion of microcracks with ages due to autogenous shrinkage or
expansion effect induced by the continuing hydration of cement
and pozzolanic reaction of mineral admixtures in the hardened
UHPC matrix with a dense microstructure [52,53]. This tendency
was found in UHPC mortar matrix without reinforcement of steel
fibers in this study and it may be alleviated by the addition of fibers
[54].
3.2. Hydration process
3.2.1. Hydration heat
The hydration heat evolutions of UHPC paste samples incorpo-
rated with different levels of MK in the first 72 h are indicated in
Fig. 3. It can be seen that a shift to the right in kinetics is revealed
with MK dosage level, which may be ascribed to the more super-
plasticizer amount. Besides, the hydration heat peak intensity of
(b) Flexural strength
 Z. Mo et al. / Construction and Building Materials 256 (2020) 119454
Fig. 3. Results of isothermal calorimetric test in the first 72 h.
ternary paste is much lower than that of the control mixture. How-
ever, compared with that of the control mixture, the hydration
heat rate of paste blended with MK decreases more slowly with
time in the descent stage and presents higher values after 24 h.
Fig. 3(c) and (d) present the total cumulative hydration heat
evolution of pastes up to 72 h. It is analogous to the evolving ten-
dency of hydration heat rate presented in Fig. 3(a) and (b). During
the first 20 h, the gaps of cumulative heat in pastes incorporated
with MK relative to that of the reference gradually increase with
time. Oppositely, this difference gets increasingly smaller with
time after 20 h. Especially, the 72 h heat release normalized to
1 g cement increases with the MK dosage level which is in accor-
dance with the strength tendency as presented in Part 3.1.
3.2.2. Chemically bound water
The mass losses of pre-dried paste samples under 60 °C from
room temperature to 400 °C (CBW) and 400 °C to 600 °C (ABW)
are exhibited in Fig. 4. All pastes present similar CBW values at
hydration age of 1 d. With the increasing age, the CBW of pastes
blended with MK is more increased and exceeds that of the refer-
ence mixture, reflecting that the more C-S-H gel forms in MK
added pastes. The increasing tendency of CBW for blended pastes
with MK are similar and the increasing rate becomes more obvious
with the increasing MK replacement level after 28 days.
The ABW value can reflect the variation of Ca(OH)2 amount in
paste samples with curing age and MK replacement level, as shown
in Fig. 4(b). In general, the ABW value is reduced by the higher MK
5
replacement level at the same age. During the first 2 days, every
sample presents an increasing ABW with the hydration age. After
3 days, the ABW of pastes blended with MK decrease rapidly till
the age of 56 days, being related to the Ca(OH)2 consumption by
the pozzolanic reaction of MK and LS.
3.2.3. Reaction degree of MK
Fig. 5 presents the MK reaction degree (MRD) for every cement
paste sample. It can be found that the MRD value grows with the
curing age while it degrades with the higher MK replacement level.
The MRD of every sample increases very quickly during the first
7 days and then increases at an obviously slower rate with the cur-
ing age, due to the absence of free water and Ca(OH)2 inside the
specimen. This decreasing reaction rate of MK during later ages
is improved by the addition of 15 or 20% MK.
3.2.4. DTA and XRD analysis
Fig. 6 presents the DTA of paste samples with different MK sub-
stitution levels and curing ages. It can be seen that two endother-
mic peaks in DTA curves occur at 100 ~ 260 °C and 430 ~ 480 °C,
respectively. The former one can be attributed to the dehydration
of gel phases, as C–S–H, C–A–H, and C–A–S–H etc., while the latter
one is induced by the dehydration of Ca(OH)2 [55].
As shown in Fig. 6(a), the endothermic peak intensity on Ca
(OH)2 for sample PLS10 is lower than that of the blank sample at
variable curing ages while that of the gel phases presents an oppo-
site growth trend. Fig. 6(b) presents the DTA results of all samples
6 Z. Mo et al. / Construction and Building Materials 256 (2020) 119454

(a) CBW of pastes (b) ABW of pastes

Fig. 4. Chemically bound water of pastes.

(a) MRD with age (b) MRD in the first 3 days

Fig. 5. Reaction degree of MK in pastes.

(a) 0% and 10% MK samples at different ages (b) Different dosages of MK at 28 days
Fig. 6. DTA curves of hydrated pastes.

at 28 days. It can be found that the endothermic peak intensity of and related to the contribution of MK and LS to mechanical
Ca(OH)2 decreases with the higher incorporation of MK. This is strength of cement paste. The portlandite amount of pastes at
attributed to the synergistic reaction of MK, LS as well as cement, 28 days shown in Table 3 calculated with TG values also present
 Z. Mo et al. / Construction and Building Materials 256 (2020) 119454 7

Table 3
The portlandite amount of pastes at 28 days.

MK level (%) 0 5 10 15 20
Amount (g/100 g cement) 18.71 11.93 9.18 7.85 7.14

similar tendency with MK level. Reference [46] furnishes a partic-

ular introduction on the calculation of Ca(OH)2.
The XRD patterns of cement pastes blended with different sub-
stitution levels of MK are presented in Fig. 7. Fig. 8 shows the
amount evolution of Ettringite and Monocarbonate phase of pastes
with MK scale at 28 days. It can be seen that the diffraction peak
intensity of Ca(OH)2 tends to become slighter with the higher
MK substitution level and curing age, being similar with the DTA
results. Fig. 8 indicates that the ettringite (AFt) amount of pastes
increases with MK dosage. Additionally, the quantity of monocar-
boaluminate phase of pastes incorporated with not more than 5%
MK are obviously larger than that of other pastes with higher MK
additions. Similarly, the XRD patterns demonstrate that the AFm-
CO3 diffraction peak are visible in sample PLS00 and PLS05, which
is also verified by a slight peak at around 150 °C in the DTA curves
of PLS05 and the control mixture with age of 28 days in Fig. 6(b).
The hydration degree of Portland cement as well as individual
clinker mineral in each paste with variable MK level at 28 days
are provided in Fig. 9. It can be observed that the hydration degree
of each mineral such as C3S, C2S, C3A and C4AF increases with the
MK level. However, the slope of every curve decreases with MK Fig. 8. Phase evolution of pastes at 28 days.
level indicating that the growth rate of hydration degree is gradu-
ally decreased. It is worth noting that the cement hydration degree
of paste blended with 30% LS in this study is significantly higher is decreased to about 6 nm at 28 days from around 15 nm at 1 day,
than that of normal UHPC paste reported in other literatures being noticeably smaller than that of the reference sample (15 nm
[21,22], being possibly due to the coupling effect of LS and MK. at 28 days).
Combined the results on compressive strength and hydration
process, it can be obtained that the MK reaction, synergistic effect
3.2.5. Pore structure on MK and LS plays a crucial effect on the strength and gel amount
Fig. 10 presents the pore structures of cement pastes at differ- increase of UHPC pastes after 3 days. It was reported that the
ent curing ages. On the first day, it is evident that the porosity chemical reaction of MK mainly occurred 7 days later for cement
(around 22%) of paste blended with 15% MK is apparently higher pates with w/b of 0.5 [44,45]. On the other hand, other literature
than that of CLS00 mix (around 16%). With the increasing curing presented that the decreasing w/b can accelerate the pozzolanic
age, this difference is reduced and all samples present a similar reaction of MK [56], being consistent with the findings in this
porosity (12%) at 28 days. As illustrated in Fig. 10(b), the pore size study. Therefore, the synergistic effect on MK, LS and cement also
distribution of pastes at 28 days are remarkably refined by the significantly contributes to the strength gain of UHPC pastes during
higher incorporation of MK when compared with that of the blank early ages as described in Part 3.1 other than the promotion on late
mixture without MK. For instance, the critical pore radius of PLS15 age strength development. Similarly, the variation of CBW in Fig. 4

Fig. 7. XRD patterns of pastes at different curing ages.

8 Z. Mo et al. / Construction and Building Materials 256 (2020) 119454

little influenced by the dosage of MK. This is induced by the cou-

pling effect of filling and reaction of MK [36]. At the same time,
the low porosity and refined microstructure partly restrains the
precipitation of crystal phases such as CH and Mc for mixtures con-
taining high dosages of MK as demonstrated by the XRD results.
Therefore, the synergistic effect on MK and LS is significantly
restrained when the MK replacement level is larger than 5%, which
behaves different from that of normal concretes with a high w/b
[32,57].

3.3. Relationship between strength and microstructure

Fig. 11 presents the influence of chemically bound water (CBW),

Fig. 9. Cement hydration degree of pastes at 28 days.
(a) is basically consistent with that of the compressive strength in
Fig. 2(a) except for PLS20.
It is worthy of attention that when the replacement level of MK
is more than 10%, the most probable pore radius of 28-day pastes is
reaction degree of MK (MRD) and pore structures of pastes on the
compressive strength of cement mortars containing variable
dosages of MK at 28 days. It is apparently observed that the higher
dosage of MK leads to the lower content of pores ranging from
20 to 100 nm and the higher content of pores smaller than
20 nm. Fig. 11(a) reveals that the CBW of cement paste presents
a similar tendency to the compressive strength of mortar specimen
with increasing dosage of MK. Therefore, the formation content of
CSH gel plays a crucial role for the mechanical strength gain as
expected. Additionally, the decreasing percentages of pores rang-
ing from 20 to 100 nm in pastes blended with dosage of 5 ~ 20%
MK have insignificant influence on improving the compressive
strength of UHPC mortar specimens. The compressive strength of

(a) Cumulative pore volume (b) Pore size distribution

Fig. 10. Pore structures of pastes with different MK replacement level.

(a) CBW and compressive strength (b) Porosity and compressive strength
Fig. 11. The relationships among compressive strength, porosity, CBW and MRD.
 Z. Mo et al. / Construction and Building Materials 256 (2020) 119454
mortars blended with 20% MK is lower than that of other MK
added mortars at 28 days, although PLS20 paste presents a highest
CBW. It may be attributed to the variable hydration composition
and microstructure and needs to be further clarified.
It is noted that both cement hydration and MK reaction con-
tribute the CBW of cement paste blended with MK. The more reac-
tion of MK in samples PLS15 and PLS20 does not increase the total
CBW value when compared with that of PLS05 and PLS10 pastes. It
is related to the facts that the pozzolanic reaction of MK competes
with the cement clinker for free water and then the late age hydra-
tion of cement is restricted for the low w/b pastes [38]. Anyway,
regardless of the reaction degree of each ingredient, the total con-
tent of gel chemically bound water provides a good indicator for
the mechanical strength of cement mortars with a low w/b.
4. Conclusions
This study aims to investigate the effect of variable dosage of
MK (0–20%) coupled with 30% LS on the hydration process and
mechanical properties of UHPC pastes and mortars with w/b of
0.2. These results on low w/b mortar or pastes can provide useful
information for the manufacture of UHPC. Based on the above
experimental results, the following conclusions can be obtained.
1) The addition of MK reduces the 1 day mechanical strength
for UHPC mortars. However, all mortars blended with 5–
20% MK behave a higher compressive and flexural strength
than the control mix after 14 days age.
2) The higher addition of MK from 5 to 15% induces the lower
hydration heat peak and the total hydration heat release of
cement pastes with w/b of 0.2 in the first 72 h.
3) The formation of C-S-H gels in cement paste increases
rapidly with age during the first 7 days and then increases
at a lower rate. The content of CH in cement paste blended
with MK increases during the first 2 days and then signifi-
cantly decreases with age due to the pozzolanic reaction of
MK and LS.
4) The cement pates with addition of 5-20% MK behaves a com-
parable porosity at 28 days. However, the higher dosage of
MK leads to the lower value of the most probable pore
radius, indicating that the pore structure is positively
refined.
Credit authorship contribution statement
Zongyun Mo: Investigation, Data curation, Writing - original
draft, Writing - review & editing. Rui Wang: Formal analysis,
Supervision, Writing - review & editing, Funding acquisition. Xiao-
jian Gao: Conceptualization, Methodology, Supervision, Writing -
review & editing, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This work was supported by the National Key Research and
Development Program of China (No. 2017YFC0404805) and the
National Natural Science Foundation of China (No. 51578192).
9
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