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Construction and Building Materials 166 (2018) 130–140

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Construction and Building Materials


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

Analysis of hydration and strength optimization of cement-fly


ash-limestone ternary blended concrete
Xiao-Yong Wang
Department of Architectural Engineering, Kangwon National University, Chuncheon-si 24341, South Korea

h i g h l i g h t s

 Simulate the hydration of cement-fly ash-limestone ternary blends.


 Consider interactions among cement hydration, fly ash reaction, and limestone reaction.
 Evaluate the strength development of ternary blended concrete.
 Find the optimum combinations of cement, fly ash, and limestone.

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

Article history: Limestone powder improves concrete early-age strength while fly ash improves concrete late-age
Received 25 September 2017 strength due to its pozzolanic reaction. The optimal mixture of cement, fly ash, and limestone is crucial
Received in revised form 6 January 2018 for material design of ternary blended concrete. This research presents a simulation program for evalu-
Accepted 9 January 2018
ating the hydration and strength optimization of ternary blended concrete. The simulation program
begins with a kinetic hydration model which simulates the hydration of cement-fly ash-limestone tern-
ary blends. The hydration model considers the mutual effects among reactions of cement, fly ash, and
Keywords:
limestone by means of the contents of calcium hydroxide and capillary water. The individual reaction
Fly ash
Limestone
degrees of components of ternary blends are calculated from the hydration model. Furthermore, the com-
Hydration pressive strength growth of hydrating ternary blended concrete is calculated by means of gel-space ratio
Model and Powers’ strength theory. Finally, based on parameter studies, the optimal combinations of cement, fly
Strength optimization ash, and limestone at different ages are determined. The proposed numerical procedure is valuable for
making composite cements as it pertains to compressive strength and environment regulations.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction stone powder. Scholer et al. [3] found that a limestone content of
2–5% leads to the stabilization of monocarbonate and ettringite
Fly ash and limestone are more and more utilized in producing which can increase the volume of hydration products and increase
high performance concrete in the modern concrete industry. Fly the strength. Bentz et al. [4] found that nano-limestone can accel-
ash and limestone present different effects on strength develop- erate the early age hydration of cement and reduce the setting time
ment of concrete. Fly ash can enhance the long-term age strength of fly ash blended concrete. Thongsanitgarn et al. [5,6] found that
of concrete due to a pozzolanic reaction while limestone can cement-fly ash-limestone ternary blended concrete presents
enhance the young-age strength of concrete because limestone higher strength compared to cement-fly ash binary concrete. Lime-
can accelerate cement hydration. When limestone and fly ash are stone with finer particle size is effective to speed up cement-fly ash
used together, due to the synergy effect, the individual deficiencies hydration. Celik et al. [7,8] found that concrete containing high vol-
can be compensated [1]. ume fly ash and limestone has high workability, high late age
Abundant experimental and theoretical studies have been per- strength, high chloride resistance, and low global warming poten-
formed on cement-fly ash-limestone ternary blended concrete. tial. Ghrici et al. [9] found that natural pozzolana did not change
Weerdt et al. [2] found that the additional aluminum from the the sulfate resistance of limestone cement, natural pozzolana
fly ash pozzolanic reaction amplified the chemical reaction of lime- improved hydrochloric acid resistance, and limestone improved
sulfuric acid resistance.

E-mail address: wxbrave@kangwon.ac.kr

https://doi.org/10.1016/j.conbuildmat.2018.01.058
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140 131

Compared with abundant experimental studies of ternary temperature on rate of hydration of cement is recognized as fol-
blended concrete [2–9], theoretical studies of ternary blended con- lowing Arrhenius’s law [14–16]. For high strength concrete, degree
crete are relatively limited. Gao et al. [10] put forward an analytical of hydration is reduced due to the withdrawal of capillary water.
modeling about the hydration of cement-slag-limestone blends. The water withdrawal mechanism is considered through ðSw =S0 Þ
The local water to cement ratio and water transport in the interfa- and C wfree in Eq. (1). ðSw =S0 Þ describes the decrease in contact area
cial transition zone was simulated. Maekawa et al. [11] proposed a between cement particle and ambient capillary water, and C wfree
computational platform which can assess the time-dependent describes the decrease in capillary water concentration.
mechanics and durability mechanics of concrete structures. The Similarly with hydration of cement, fly ash reaction also con-
couplings among hydration, mass transport, and damage evolution sists of three stages [14–16], initial dormant stage, chemical-
were considered. However, Gao et al. [10] and Maekawa et al.’s reaction related stage, and diffusion related stage. In addition, fly
[11] studies do not consider the chemical reaction of limestone ash reaction is dependent on calcium hydroxide content in
in ternary blended concrete. Bentz [12] proposed a model which cement-fly ash binary blends. The equation of fly ash reaction is
simulated the dilution, nucleation, and chemical effects of lime- simplified written as below [14–16]:
stone additions in cement-limestone binary blends. Weerdt et al.
daFA mCH ðtÞ
[13] made a thermodynamic modeling of hydration of cement-fly ¼ f ðkdFA ðTÞ; DeFA ðTÞ; krFA ðTÞ; r FA0 Þ  ð2Þ
ash-limestone ternary blends. The volumetric phase fractions of dt P
the hydrating paste were calculated using Gibbs Energy Minimiza- where dadtFA is fly ash reaction rate, kdFA is rate of coefficient in initial
tion Software (GEMS) program. However, the thermodynamic dormant stage of fly ash, DeFA is rate of coefficient in diffusion
modeling in the Weerdt et al. study [13] mainly focuses on the
related stage of fly ash, krFA is rate of coefficient in reaction related
chemical aspects of ternary blended concrete. Regarding the opti-
stage of fly ash, r FA0 is unreacted fly ash particles radius, mCH ðtÞ is
mal combinations of cement, fly ash, and limestone in ternary
the content of calcium hydroxide, P is fly ash content in proportions
blended concrete, current models [10–13] still do not cover this
of concrete mix.
point.
The time-dependent cement or fly ash reaction degrees can be
To avoid the flaws of current studies, this research presents a
calculated using the cement-fly ash binary hydration model. In
hydration based simulation program to assess the strength growth
addition, the thermal properties, mechanical properties, and dura-
and optimal combinations of ternary blended concrete. The
bility of fly ash blended concrete can be evaluated using reaction
strength is evaluated considering the influences from reactions of
degree of individual component of binders. The cement-fly ash bin-
cement, fly ash, and limestone. The optimal combinations are
ary hydration model is multiply validated using experimental data
determined based on parameter studies of the hydration-
for concrete with various proportions of mix and curing conditions.
strength integrated model.
However, because the cement-fly ash binary hydration model does
not consider the effect of limestone, binary hydration model can-
2. Simulation of the hydration of cement-fly ash-limestone not analyze the hydration of cement-fly ash-limestone ternary
ternary blends concrete.

2.1. Simulation of the hydration of cement-fly ash binary blends 2.2. Limestone powder reaction mode

Our previous studies [14–16] presented a kinetic hydration Bentz [12] reported that the addition of limestone presents
model for concrete containing fly ash. This kinetic hydration model dilution, nucleation, and chemical effects on cement hydration.
includes three sub-models, i.e. model for hydration of cement, The dilution effect happens when limestone substitutes partial
model for reaction of fly ash, and model for mutual effects between cement, cement content decreases and water to cement ratio
reactions of cement and fly ash. The cement hydration model con- increases correspondingly. The nucleation effect is the fact that
siders the kinetic stages involved in the hydration of cement, such limestone may work as a nucleation site of hydrating
as initial dormant stage, chemical-reaction related stage, and diffu- cement. Hydration of cement can accelerate due to the nucle-
sion related stage. The cement hydration model also considers the ation effect. The chemical effect is the formation of monocar-
water withdrawal on account of the lack of capillary water regard- boaluminate due to the limestone reaction in preference to a
ing high strength concrete. The equation of cement hydration is monosulfoaluminate.
simplified and written as follows [14–16]: In this research, the dilution effect of limestone powder can be
C0
considered by W term in C wfree of Eq. (1). Regarding the nucleation
da 0
¼ f ðkd ðTÞ; De ðTÞ; kr ðTÞ; r0 Þ  C wfree  ðSw =S0 Þ ð1Þ effect, Maekawa et al. [11] and Wang [16] proposed that the nucle-
dt
ation effect of limestone relates to the ratio of surface area of
where ddta is rate of hydration, kd is rate of coefficient in initial dor- cement particles to that of limestone powder. The nucleation effect
mant stage, T is curing temperature, kr is rate of coefficient in reac- indicator of limestone powder can be written as follows [16]:
tion related stage, De is rate of coefficient in diffusion related stage,
LS0  SLS
r 0 is unreacted cement particles radius, Sw means the effective con- Lr ¼ ð3Þ
C 0  SC
tact area between the surrounding capillary water and cement par-
ticles [14–16], S0 means the total area if cement hydration products where Lr denotes the indicator of the nucleation effect from lime-
progress unconstrained, C wfree is capillary water content stone addition, LS0 denotes the limestone mass in proportions of
 r
(C wfree ¼ W 0 0:4C 0a
where C 0 is cement content in concrete mix- concrete mix, SLS denotes the specific surface (Blaine) of limestone,
W0
and SC denotes the specific surface (Blaine) of cement. Maekawa
ing proportions, W 0 is the content of water in the proportions of et al. [11] reported that the nucleation effect of limestone is signif-
concrete mix, r (r ¼ 2:6  4 W
C0
0
) is an empirical factor considering icant in the reaction related stage and the diffusion related stage. In
the approachability of capillary water from outer hard shell to inner our former study [16], based on the experimental data of hydration
anhydrous part of cement particles). degree of cement in cement-limestone binary blends, Wang [16]
The rate coefficients kd , kr , and De can be determined based on proposed that the nucleation effect of limestone powder can
compound compositions of cement [14–16]. The effect of described as follows:
132 X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140

krLS ¼ kr ð1 þ 1:2Lr Þ ð4Þ to binder ratio, and curing temperature, will affect the limestone
reaction [19,20]. Considering these points, we propose a more
DeLS ¼ De ð1 þ 1:2Lr Þ ð5Þ general equation for determining the reaction degree of limestone
as follows:
where krLS is the updated phase boundary reaction coefficient in
cement-limestone blends, 1.2 is enhance coefficients of kr [16], aLS ¼ aLS1  m1  m2  m3  m4  m5  m6 ð7Þ
DeLS is the updated diffusion coefficient in cement-limestone blends,
and 1:2 is enhance coefficients of De [16]. where m1 considers the effect of limestone replacement ratios on
Ipavec et al. [17] measured the formation of carboaluminate reaction degree of limestone, m2 considers the effect of limestone
phases in limestone powder blended paste (the water to binder fineness, m3 considers the effect of cement fineness, m4 considers
ratio is 0.5, the limestone replacement ratio is 0.2, and curing tem- the effect of fly ash addition, m5 considers the effect of water to bin-
perature is 20 °C). The contents of carboaluminate phases were der ratio, and m6 considers the effect of curing temperature. For the
measured at 1, 3, 7, 15, 28, and 100 days. Monocarboaluminate is case of Ipavec et al.’s [17] study, all of these influencing factors
the main hydration product of limestone at late ages. Based on equal to 1.
monocarboaluminate contents, we suggest that the limestone
reaction degree can be calculated as below: 2.2.1. Effect of limestone replacement ratios
Antoni et al. [20] reported that as limestone replacement ratio
aLS1 ¼ 0:0087 lnðtÞ  0:0265 ðt > 21Þ ð6Þ increases, the reaction degree of limestone powder decreases.
where aLS1 is the reaction degree of limestone powder, and t is age Based on Antoni’s [20] results, we found that the reaction degree
(hours). The evaluation results about reaction degree of limestone of limestone is approximately an inverse proportional function of
are shown in Fig. 1. Fig. 1 shows that the reaction degree of limestone replacement ratio. Hence, we assume that m1 ¼ 0:2 LS0 .
C 0 þLS0
limestone is a logarithm function of time, which is similar to the
relation between hydration degree of cement and curing age
2.2.2. Fineness of limestone
[14–16]. Fig. 1 also shows that the reaction of limestone starts after
Aqel and Panesar [19] reported that when average particle size
about 21 h, not immediately after mixing. Bentz [12] proposed that
of limestone powder decreases, the reactivity of limestone
the limestone chemical reaction can be written as 3ðCaOÞ3 ðAl2 O3 Þ
increases. Based on Aqel’s study [19] about the relation between
CaSO4  12H2 O þ 2CaCO3 þ 18H2 O ! 2ðCaOÞ3 ðAl2 O3 Þ  CaCO3  11H2 O þ
reaction degree and particle size of limestone, we assumed that
ðCaOÞ3 ðAl2 O3 Þ  3CaSO4  32H2 O. Bentz’s [12] study shows that the
m2 ¼ 1:0131  0:0144  dLS where dLS is average diameter of
limestone reaction starts only when the initial calcium sulfate
limestone.
is fully consumed and the formed ettringite phase begins to convert
to the AFm phase. Lothenbach [18] reported that after about 1 day,
the reaction of limestone starts. The starting time of limestone in 2.2.3. Fineness of cement
Lothenbach’s [18] study (1 day) is similar to our study (21 h). In Aqel and Panesar [19] found that when the Blaine surface of
addition, by using Eq. (6), we find that at the age of 180 days, the cement increases, the average reaction degree of limestone also
reaction degree of limestone is about 4.6%, which is similar to increases. Based on Aqel’s [19] study, we assumed that that
the results of Bentz’s study [12] (Bentz [12] proposed that for m3 ¼ 0:55 SSC1C þ 0:45 where SC1 is the Blaine surface of cement used
concrete with 20% limestone, at the age of 180 days, about 5% in Ipavec et al.’s [17] study.
limestone reacted). The reactivity of limestone is much lower
compared to cement or fly ash [14–16]. 2.2.4. Fly ash additions
On the other hand, we should notice that Eq. (12) is only valid Weerdt et al. [2] reported that due to the high aluminum con-
for Ipavec et al.’s [17] study (water to binder ratio was 0.5, lime- tent in fly ash, the limestone reaction in cement-fly ash-
stone replacement ratio was 0.2, and curing temperature was limestone ternary blends is enhanced. We proposed that the influ-
_20 °C). Limestone reaction is a complex process and relates to ence of fly ash on limestone addition can be described as
abundant factors. The factors, such as limestone replacement
m4 ¼ 1 þ AlAlFAC aaCFA0P, where AlFA and AlC are aluminum contents in fly
ratios, fly ash addition, limestone fineness, cement fineness, water
ash and cement respectively. AlFA aFA P and AlC aC 0 are reacted alu-
minum contents from fly ash reaction and cement reaction
respectively.

2.2.5. Water to binder ratios


Similar with cement hydration, the reaction products of lime-
stone deposits in the pore space of concrete. We assumed that
when the water to binder ratio increases, the reaction degree of
limestone increase consequently. We proposed that m5 ¼ aa0:5
where a0:5 is reaction degree of cement for the case of water to bin-
der ratio 0.5.

2.2.6. Curing temperature


Curing temperature presents a two-sided effect on limestone
reactivity. First, as curing temperature increases, the solubility of
limestone decreases which will lower limestone reactivity. How-
ever, cement hydration is accelerated due to the curing tempera-
ture increasing. The increasing of cement reactivity may increase
limestone reactivity. Aqel and Panesar [19] found that compared
to other factors, such as moist curing duration, cement fineness,
Fig. 1. Reaction of limestone. and limestone content, the influence of curing temperature on
X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140 133

Table 1 on experimental results of Weerdt et al. [13], we proposed that


Summary of influencing factors of limestone reaction. when 1 g of limestone reacts, 0.35 g of calcium hydroxide will be
Factor Equation Influencing trend consumed. Regarding cement-fly ash-limestone ternary blends,
Limestone m1 ¼ 0:2 As limestone replacement CH content can be determined as below:
LS0

ratio increases, aLS decreases


CHðtÞ ¼ RCHCE  C 0  a  v FA  aFA  P  0:35  aLS  LS0
C 0 þLS0
replacement
ð10Þ
ratios
Fineness of m2 ¼ 1:0131  0:0144 dLS As fineness of limestone where RCHCE means the produced CH as 1 unit mass of cement
increases, aLS increases
hydrates, v FA means the consumed CH as 1 unit mass of fly ash
limestone
Fineness of m3 ¼ 0:55 SSC1C þ 0:45 As fineness of cement
cement increases, aLS increases reacts. RCHCE  C 0  a is the produced CH from cement hydration.
Fly ash m4 ¼ 1 þ AlFA aFA P
AlC aC 0
As fly ash addition increases, v FA  aFA  P and 0:35  aLS  LS0 are the consumed CH from reactions
additions aLS increases of fly ash and limestone respectively.
Water to binder m5 ¼ aa0:5 As water to binder ratio Summarily, from Sections 2.1–2.3, a simulation program is put
ratios increases, aLS increases
Curing m6 ¼ 1 Curing temperature do not
forward which simulates the hydration of cement-fly ash-
temperature influence aLS limestone blends. The interactions among reactions of cement, fly
ash, and limestone are taken into account by means of the contents
of calcium hydroxide and capillary water. This simulation program
limestone reactivity is marginal. Based on Aqel and Panesar’s [19] considers the dilution, nucleation, and chemical effects from fly ash
results, we approximately assumed the m6 ¼ 1: and limestone additions. The input parameters of this numerical
The summaries of influencing factors of limestone reaction are procedure are concrete mixing proportions, physical and chemical
shown in Table 1. Our proposed model considers the dilution, properties of binders, and curing conditions. Furthermore, by using
nucleation, and chemical effects of limestone. We consider dilution kinetic reaction equations, the time-dependent reaction degrees of
C0 individual components can be determined. In addition, it should be
effect through capillary water concentration (W term in C wfree of
0
noticed that the reaction coefficients of proposed ternary hydration
Eq. (1)). We consider nucleation effect through nucleation effect
model do not vary with proportions of concrete mix. As the combi-
indicator (Eq. (3)). We consider chemical effect using a logarithm
nations of cement, fly ash, limestone, and water change from one
function and multiple modification factors (Eqs. (6) and (7)). The
mix to another, the reaction coefficients of ternary hydration
modification factors reflect the general trends of reaction degree
model are constant.
of limestone powder. However, because the available experimental
results about reaction degree of limestone are very limited, the cal-
2.4. Compressive strength development model
ibrations of modification factors still need further study. Other
influencing factors, such as the aluminum and gypsum content in
The products of the reaction of cement, fly ash, and limestone
cement, also need more study. The heat liberation by limestone
powder will fill the pore space of concrete. Concrete compressive
reaction is not considered in the current study.
strength develops with the progress of binders reaction. According
to Powers’ strength theory, concrete compressive strength can be
2.3. Interactions model among reactions of cement, fly ash, and evaluated as below:
limestone
f c ðtÞ ¼ Axnc ð11Þ
In this study, the contents of calcium hydroxide (CH) and capil- where f c ðtÞ is concrete compressive strength, A is the intrinsic
lary water of hydrating ternary blends are adopted as fundamental strength of concrete, xc is gel-space ratio of concrete, and n is the
indicators to consider mutual interactions among reactions of strength exponent. The gel-space ratio denotes the volumetric ratio
cement, fly ash, and limestone. Bentz [12] proposed that when 1 of binder hydration products to the sum of hydrated binders and
g limestone powder reacts, 1.62 g of water will be consumed. capillary pore. For cement-fly ash-limestone blends, 1 ml hydrated
The consumed water of limestone power is much higher compared cement occupies 2.06 ml of space [21–24], 1 ml reacted fly ash
to cement or fly ash. This is because the reaction products of lime- occupies 2.52 ml space [21–24], and 1 ml reacted limestone occu-
stone powder are monocarboaluminate and ettringite which con- pies 4.1 ml space [12]. Reacted products of 1 ml limestone can
tain abundant water. For cement-fly ash-limestone ternary occupy much higher space that that of cement (4.1 vs. 2.06). This
blends, the content of capillary water W cap can be determined as is because of the formation of ettringite and monocarboaluminate
below: from the limestone reaction. Considering the reactions of cement,
W cap ¼ W 0  0:4  C 0  a  0:25  aFA  P  1:62  LS0  aLS ð8Þ fly ash, and limestone, the gel-space ratio of cement-fly ash-
limestone ternary blended cement can be determined as follows:
where 0:4  C 0  a, 0:25  aFA  P; and 1:62  LS0  aLS are the con-
2:06ð1=qC ÞaC 0 þ 2:52ð1=qFA ÞaFA P þ 4:1ð1=qLS ÞaLS LS0
sumed water from reactions of cement, fly ash, and limestone xc ¼ ð12Þ
respectively. ð1=qC ÞaC 0 þ ð1=qFA ÞaFA P þ ð1=qLS ÞaLS LS0 þ W 0
Cement hydration, fly ash reaction, and limestone reaction will where qFA and qLS are density of fly ash and limestone powder
contribute to the formation of chemically bound water. The chem- respectively.
ically bound water W cbm can be determined as follows: For ternary blends, individual binder component will affect the
W cbm ¼ v  C 0  a þ 0:1  P  aFA þ 1:62  LS0  aLS ð9Þ intrinsic strength of concrete and strength exponent. We assume
that the intrinsic strength of concrete A and strength exponent n
where v  C 0  a, 0:1  P  aFA ; and 1:62  LS0  aLS are the contents of can be written as functions of weight percentages of cement, fly
produced chemically combined water from reactions of cement, fly ash, and limestone in the proportions of mix as follows:
ash, and limestone respectively.
C0 P LS0
Weerdt et al. [13] measured calcium hydroxide contents for A ¼ a1 þ a2 þ a3 ð13Þ
hydrating cement-limestone blends. They found that the calcium
C 0 þ P þ LS0 C 0 þ P þ LS0 C 0 þ P þ LS0
hydroxide (CH) content in limestone blended concrete is lower
C0 P LS0
compared to control specimen. CH is consumed on account of n ¼ b1 þ b2 þ b3 ð14Þ
C 0 þ P þ LS0 C 0 þ P þ LS0 C 0 þ P þ LS0
the production of hemicarbonate from limestone reaction. Based
134 X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140

where coefficients a1 a2; and a3 in Eq. (13) denote the influences of


Se
cement, fly ash, and limestone towards the intrinsic strength of con-
crete, respectively, and the units of a1, a2, and a3 are MPa; the coef-
ficients b1, b2 and b3 in Eq. (14) denote the influences of cement, fly
ash, and limestone towards strength exponent, respectively. For
neat Portland cement concrete, the weight fractions of limestone
or fly ash are zero, the strength of concrete only relates to a1 and
b1. For fly ash blended binary concrete, the weight fraction of lime-
stone is zero, and the strength of concrete relates to coefficients a1,
a2, b1, and b2. For ternary blended concrete, concrete strength
depends to coefficients a1, a2, a3, b1, b2, and b3. These coefficients
a1, a2, a3, b1, b2, and b3 do not change for various concrete
mixtures.
The flowchart of the calculation is shown in Fig. 2. At every time
step, the reaction degrees of individual components are calculated
by using the ternary blended hydration model. The contents of CH,
chemically combined water, and capillary water are determined by
using reaction degrees of binders. Furthermore, the gel-space ratio
of hydrating concrete is calculated taking into account the contri-
butions from reactions of cement, fly ash, and limestone. By using
Powers’ strength theory, concrete compressive strength is
calculated.

3. Verifications of proposed model

Experimental results from references [2,13] about strength and


reaction degrees of binders in ternary blended concrete are used to
validate the proposed hydration-strength integrated model. Table 2
shows the mixtures of specimens. Table 3 shows the chemical
compositions and physical characteristics of cement, fly ash, and
limestone. Regarding the compressive strength, a total of 21 mix-
ing proportions are used including control specimen, limestone
blended binary mortar, fly ash blended binary mortar, and ternary
blended mortar. The replacement ratio for limestone or fly ash in
Fig. 2. Flowchart of simulation.
binary blended specimen ranged between 5% and 35%. The replace-
Table 2 ment ratio of mineral admixtures in ternary blended specimen was
Mixing proportions of mortar specimens. 35% (the fly ash or limestone content ranged between 5% and 30%,
and the sum of contents of fly ash and limestone was constant at
Mortar Portland cement (%) Fly ash Limestone Water to power ratio
(%) (%) 35%). The specimens for compressive strength measurement were
mortar specimen, and the specimens for degree of reaction were
1 100 0 0 0.5
2 95 0 5 0.5 paste specimen. For mortar specimen, the sand to power ratio
3 90 0 10 0.5 was 3:1. At the ages of 1, 28, 90, and 140 days, the compressive
4 85 0 15 0.5 strength was measured. For paste specimen (corresponding
5 80 0 20 0.5 to specimens No. 1, 2, 15, 16 in Table 2), the cement and fly ash
6 75 0 25 0.5
7 70 0 30 0.5
reaction degrees were measured at the age of 1, 7, 28, 90, and
8 65 0 35 0.5 180 days.
9 95 5 0 0.5
10 90 10 0 0.5
11 85 15 0 0.5 3.1. Hydration reaction of ternary blends
12 80 20 0 0.5
13 75 25 0 0.5 Based on the hydration model and specimen mixtures, the
14 70 30 0 0.5 development of reaction degree of cement, fly ash, and limestone
15 65 35 0 0.5
can be calculated. Fig. 3 shows hydration related properties of
16 65 30 5 0.5
17 65 25 10 0.5 cement-fly ash-limestone blends. As shown in Fig. 3a, compared
18 65 20 15 0.5 to the control specimen, reaction degree of cement in cement-
19 65 15 20 0.5 limestone binary blends (95% cement + 5% limestone) is slightly
20 65 10 25 0.5
higher. This is because of the dilution and nucleation effects from
21 65 5 30 0.5
limestone addition. In cement-fly ash binary blends (65% cement

Table 3
Properties of binders.

SiO2 Al2O3 Fe2O3 CaO MgO SO3 K2O Na2O Blaine surface
(%) (%) (%) (%) (%) (%) (%) (%) (m2/kg)
Cement 20.0 5.4 3.1 60.6 2.9 1.5 1.2 0.5 450
Fly ash 50.0 23.9 6.0 6.3 2.1 0.4 1.4 0.6 450
Limestone 12.9 2.7 2.0 42.3 1.8 – 0.6 0.5 810
X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140 135

100 50
control FA35%-cal
reaction degree of cement %

reaction degree of fly ash %


LS5% FA35%-expe
80 40
FA35% FA30%+5%LS-cal
FA30%+5%LS FA30%+5%LS-expe
60 exper. res 30

40 20

20 10

0 -2 0 2 4
0 0 2 4
10 10 10 10 10 10 10
curing age(hours) curing age(hours)

(a)Reaction degree of cement. (b) Reaction degree of fly ash.


limestone binary blended concrete
0.2

reaction degree of limestone powder


0.15 LS5%
LS15%
LS25%
LS35%
0.1

0.05

0
0 1000 2000 3000 4000 5000
curing age(hours)

(c)CH content in cement-limestone (d) Reaction degree of limestone in


binary blends. cement-limestone binary blends.
cement 65%+FA 20%+Limestone15%
1 unhydrous cement
unreacted fly ash
0.8 unreacted limestone
phase volume fractions

cement hydration products


fly ash reaction products
0.6 limestone reaction products
porosity

0.4

0.2

0 0 2
10 10
time(hours)

(e) Reaction degree of limestone in (f) Phase volume fractions of ternary


ternary blends
. blends
.
Fig. 3. Hydration of cement-fly ash-limestone ternary blended cement.

+ 35% fly ash), due to the dilution effect from fly ash addition, blends. The sequence of reaction degree of cement from high to
cement reaction degree is higher than control paste. The ternary low is ternary blends, fly ash binary blends, limestone binary
blends (65% cement + 30% fly ash + 5% limestone) has a higher blends, and control specimen. The proposed hydration model can
reaction degree of cement than the control specimen or binary reproduce this sequence of reaction degree of cement.
136 X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140

Fig. 3b shows fly ash reaction degree in binary or ternary lower compared to binary mix (5% limestone + 95% cement). This is
blended concrete. When 5% limestone is added, the fly ash reaction because the cement to limestone ratio is lower in ternary mix
degrees in binary blends (65% cement + 35% fly ash) or ternary compared to binary mix (related to influencing factor m1 of
blends (65% cement + 30% fly ash + 5% limestone) are similar. First, limestone reaction).
the limestone addition can lower CH content which will decrease Based on reaction degree of binders and volumetric ratio
the rate of fly ash reaction. Second, when partial fly ash is replaced between reaction products and binders, the volumetric phase frac-
by limestone, the ratio between cement and fly ash increases tions of hydrating ternary paste can be calculated. Fig. 3f shows the
which will increase the rate of fly ash reaction. On account of the volumetric phase fractions of ternary paste (cement 65% + fly ash
simultaneous effects of increasing factor and decreasing factor, 20% + limestone 15%). Because cement hydrates much quicker
fly ash reaction degrees in binary blends or ternary blends are compared to fly ash, less cement is remained compared to fly
similar. ash. On account of the depositing of reaction products, capillary
Fig. 3c shows CH content in limestone binary blends (95% porosity decreases as hydration evolves.
cement + 5% limestone) and control concrete. On account of the
consumption of CH from limestone addition, limestone binary 3.2. Strength development and strength optimization of concrete
blends present lower CH contents compared to control
specimen. Fig. 3d shows that regarding cement-limestone binary Based on the reaction degree of binders, the gel-space ratio of
blends, the reaction degree of limestone decreases as limestone hardening concrete can be determined. Moreover, concrete com-
content increases. Fig. 3e shows that at late age, fly ash (5% pressive strength can be calculated using Powers’ strength theory.
limestone + 30% fly ash + 65% cement) can increase the reaction By using experimental data of concrete compressive strength with
degree of limestone compare to limestone-cement binary blends various mixing proportions at different ages, these coefficients a1,
(5% limestone + 95% cement). This is because of the high aluminum a2, a3, b1, b2, and b3 can be calibrated. The values of intrinsic
content in fly ash (related to influencing factor m4 of limestone strength of cement, fly ash, and limestone are 184.89 MPa,
reaction). While at early-age, limestone powder reaction degree 207.11 MPa, and 122.09 MPa respectively. The values of strength
in ternary mix (5% limestone + 30% fly ash + 65% cement) is slightly exponent of cement, fly ash, and limestone are 2.45, 3.04, and

limestone binary blended concrete limestone binary blended concrete


1 1.5
relative reaction degree of cement
reaction degree of cement

0.8
OPC
10%ls 1
0.6 20%ls
30%ls OPC
10%ls
0.4 20%ls
0.5 30%ls

0.2

0 0
0 50 100 150 200 0 50 100 150 200
curing age(days) curing age(days)

(a)Reaction degree of cement. (b) Relative reaction degree of cement.

limestone binary blended concrete limestone binary blended concrete


70 control 1.5
5%LS
relative compressive strength

60
compressive strength(MPa)

10%LS
15%LS
50
20%LS 1
25%LS
40
30%LS
35%LS
30
exper. res.
0.5 OPC
20
10%ls
20%ls
10
30%ls
0 -1 0 1 2
0 -1 0 1 2
10 10 10 10 10 10 10 10
curing age(days) curing age(days)

(c) Compressive strength. (d)Relative compressive strength.


Fig. 4. Strength evaluation of cement-limestone binary blends.
X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140 137

2.39 respectively. These coefficients do not change for various mix- from that of relative compressive strength (Fig. 4d). The compres-
ing proportions of concrete (total 21 mixtures) and various curing sive strength relates to not only degree of hydration, but also the
ages (from early age (1 day) to late ages (28, 90, and 140 days)). A contents of cement and limestone.
total of 84 experimental data about compressive strength (21 * 4 = The analysis of strength development of cement-fly ash binary
84) are used in this research. blends is shown in Fig. 5. Fig. 5a shows fly ash reaction degree in
The development of strength of cement-limestone binary binary blends. As fly ash content increases, the alkali activation
blends is shown in Fig. 4. Fig. 4a shows cement reaction degree effect becomes weaker, and fly ash reaction degree decreases.
in cement-limestone binary blends. As limestone content Fig. 5b shows that the analysis results generally conform to exper-
increases, due to dilution effect and nucleation effect, cement imental data. Fig. 5c shows that at early-age, fly ash additions
hydration degree increases. In this study, the relative hydration lower concrete strength. This is because fly ash reaction rate is
degree of cement means the ratio of hydration degree of cement much lower compared to cement (shown in Fig. 3b and a). While
in binary blends to that in plain specimen, and the relative strength at late age, due to the progress of the fly ash reaction, the strength
means the ratio of compressive strength of binary blends to that of of concrete containing fly ash can surpass the strength of plain con-
plain specimen. As shown in Fig. 4b, as limestone content crete. As fly ash content increases, fly ash reaction degree becomes
increases, relative reaction degree of cement also increases. lower (shown in Fig. 5a), and age akin to exceed strength is going
Fig. 4c shows that the analysis results about compressive strength to be delayed.
generally conform to experimental data. Fig. 4d shows that at Fig. 6 presents the analyzed compressive strength of ternary
early-age, limestone addition can increase concrete strength. This blends. At long term age, the specimens containing higher fly ash
is because of the acceleration of hydration of cement. While at late content (Fig. 6a and b) have higher compressive strength than
age, due to dilution effect, limestone blended concrete presents those containing lower fly ash contents (Fig. 6e and f). The results
lower strength compared to control concrete. It should be noted of analysis and tests are shown in Fig. 7. The relative coefficient
that the trend of relative degree of hydration (Fig. 4b) is different between analysis and experiment results is 0.99, and the root

fly ash binary blended concrete fly ash binary blended concrete
1 70 control
10%Fa
5%FA
20%Fa 60
compressive strength(MPa)

10%FA
reaction degree of fly ash

0.8 35%Fa
15%FA
50
20%FA
0.6 25%FA
40
30%FA
30 35%FA
0.4 exper. res.
20
0.2
10

0 -1 0 1 2
0 -1 0 1 2
10 10 10 10 10 10 10 10
curing age(days) curing age(days)

(a)Reaction degree of fly ash. (b)Compressive strength.

fly ash binary blended concrete


1.5
relative compressive strength

OPC
10%Fa
0.5 20%Fa
35%Fa

0 -1 0 1 2
10 10 10 10
curing age(days)

(c)Relative compressive strength.


Fig. 5. Strength evaluation of cement-fly ash binary blends.
138 X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140

mean square error (RMSE) between analysis and experiment is Based on the hydration-strength integrated model, we perform
1.48 MPa. The analysis results generally conform to the experi- parameter studies about strength of ternary blended concrete with
mental data. The proposed simulation program can evaluate the various binder combinations at various ages. As shown in Fig. 8a
strength of binary and ternary concrete at both early ages and late (0.3 day) and Fig. 8b (0.5 day), because limestone addition can
ages. improve concrete early age strength, concrete with higher

LS 5%+ FA30% LS 10%+ FA 25%


70 70
analysis analysis
60 experiment 60 experiment
compressive strength(MPa)

compressive strength(MPa)
50 50

40 40

30 30

20 20

10 10

0 -1 0 1 2
0 -1 0 1 2
10 10 10 10 10 10 10 10
curing age(days) curing age(days)

(a) LS 5%+FA 30%. (b) LS 10%+FA 25%.


LS 15%+ FA 20% LS 20%+ FA15%
70 70
analysis analysis
60 experiment 60 experiment
compressive strength(MPa)

compressive strength(MPa)

50 50

40 40

30 30

20 20

10 10

0 -1 0 1 2
0 -1 0 1 2
10 10 10 10 10 10 10 10
curing age(days) curing age(days)

(c) LS 15%+FA 20%. (d) LS 20%+FA 15%.


LS 25%+ FA 10% LS 30%+ FA 5%
70 70
analysis analysis
60 experiment 60 experiment
compressive strength(MPa)

compressive strength(MPa)

50 50

40 40

30 30

20 20

10 10

0 -1 0 1 2
0 -1 0 1 2
10 10 10 10 10 10 10 10
curing age(days) curing age(days)

(e) LS 25%+FA 10%. (f) LS 30%+FA 5%.


Fig. 6. Strength evaluation of ternary blends.(a) LS 5%+FA 30%. (b) LS 10%+FA 25%. (c) LS 15%+FA 20%. (d) LS 20%+FA 15%.
X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140 139

70 12

optimum limestone replacement ratio %


LS binary blended concrete
60 FA binary blended concrete
10 0.3 day
ternary blended concrete
analysis results(MPa)

50
8
40
6
30 0.5 day
4 28 days 90 days
20

10 2

0 0
0 10 20 30 40 50 60 70 0 5 10 15 20 25
experimental results(MPa) optimum fly ash replacement ratio %

Fig. 7. Comparison between analysis and experimental results. Fig. 9. Optimum combinations of ternary blends.

limestone content and lower fly ash contents has the highest the highest strength of all mixes. As shown in Fig. 9, from early-
strength of all other mixes. As shown in Fig. 8d (90 days), because age to late age, the optimal combination for ternary blends shifts
fly ash can improve concrete late age strength, concrete with from high limestone-low fly ash zone to high fly ash-low limestone
higher fly ash contents and lower limestone contents presents zone.

11
25 25 15
fly ash replacement ratio %

fly ash replacement ratio %

10 14
20 20
13
9
15 15
12
8
10 10 11

7 10
5 5
9
6
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
limestone replacement ratio % limestone replacement ratio %
(a) 0.3 day. (b)0.5 day.

25 48 25 57
fly ash replacement ratio %

fly ash replacement ratio %

56
20 46 20
55

44 54
15 15
53
10 42 10 52
51
5 40 5
50

0 38 0 49
0 2 4 6 8 10 12 0 2 4 6 8 10 12
limestone replacement ratio % limestone replacement ratio %

(c) 28 days. (d) 90 days.


Fig. 8. Parameter studies of strength of ternary blends.
140 X.-Y. Wang / Construction and Building Materials 166 (2018) 130–140

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