Construction and Building Materials 242 (2020) 118029

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Construction and Building Materials

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Rheology, shrinkage and pore structure of alkali-activated slag-fly ash

mortar incorporating copper slag as fine aggregate
Nanqiao You a, Yongchao Liu a, Dawei Gu b, Togay Ozbakkaloglu c, Jinlong Pan b, Yamei Zhang a,⇑
a
School of Materials Science and Engineering, Jiangsu Key Laboratory of Construction Materials, Southeast University, Nanjing 211189, China
b
School of Civil Engineering, Southeast University, Nanjing 211189, China
c
Ingram School of Engineering, Texas State University, TX 78666, USA

h i g h l i g h t s

CS was used as fine aggregate to replace NS at different levels in AASF mortars.

Using CS at proper levels restrains drying shrinkage and refines the pore structure.

AASF mortars obtain poor performance when the replacement of CS is high.

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

Article history: his study was conducted to investigate the effect of the use of copper slag (CS) as fine aggregate to replace
Received 27 September 2019 natural sand (NS) at different volume replacement levels (namely, 0%, 20%, 40% and 60%) on the proper-
Received in revised form 7 December 2019 ties of alkali-activated slag-fly ash (AASF) mortars. In addition, both low calcium (LC) and high calcium
Accepted 2 January 2020
(HC) alkali-activated slag-fly ash (AASF) mortars were used to studied the influence of the mass ratio
Available online 16 January 2020
of fly ash to fly ash and slag on the properties of mortars. The workability, mechanical properties, auto-
genous and drying shrinkage and pore structure of mortars were investigated. Results show that using CS
Keywords:
to replace NS in AASF mortars at appropriate levels (i.e. 20% and 40%) slightly increases the fluidity, yield
Activated slag-fly ash mortar
Copper slag
stress, consistency, and mechanical strength, while restraining the drying shrinkage and refining the pore
Fine aggregate structure of mortars. However, when the replacement ratio is increased to 60%, the mortar becomes inho-
Rheology mogeneous due to the high density of CS particles, leading to poor performance of mortars. The use of CS
Mechanical strength as fine aggregate at a suitable level in AASF mortars can reduce NS consumption while also providing an
Shrinkage avenue for value added use of CS.
Pore structure Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction ucts are amorphous sodium alumina silicate hydrate (N-A-S-H)

It has been recognised for decades that alkali-activated cemen-
titious materials (AAMs) are being deliberated as a potential alter-
nate construction material and an environment-friendly material
to Portland cement (PC) [1,2]. Alkali activation technology can
observably reduce the CO2 emission by up to 80% relative to PC
[3,4]. AAMs mixes use large amounts of ground granulated blast
furnace slag (GGBS), fly ash (FA) and other industrial by-products
as precursors [5,6]. The properties of the AAMs change significantly
because of the composition, mineralogy and particle morphology
of the precursor [7]. It was reported that the chemical reaction
products of alkali-activated GGBS are calcium alumina silicate
hydrate (C-A-S-H) gels [8], while for alkali-activated FA, the prod-
⇑ Corresponding author.
E-mail address: ymzhang@seu.edu.cn (Y. Zhang).
gels [9]. AAMs with the precursors of GGBS and FA, namely
alkali-activated slag-fly ash (AASF), are also investigated, aiming
to mitigate the disadvantages of each precursor material when
used separately in AAM. For AASF, better strengths development,
lower drying shrinkage and better resistance to aggressive chemi-
cals have been achieved compared with alkali-activated GGBS or
alkali-activated FA [4,10,11].
Copper slag (CS) is a kind of by-product produced during smelt-
ing and converting processes of copper manufacturing. It is
reported that nearly 2.2 tons of CS is generated for every ton of
copper production and around 24.6 million CS are generated annu-
ally in the world [12]. CS is rich in FeO, Fe2O3 and contains various
other elements such as Si, A1, Ca, Mg and Cu in metallic or oxide/-
sulphide forms [13]. CS possesses favourable properties like abra-
sion resistance and mechanical strength, which rise the potential
of CS application in the production of abrasive tools, pavement

https://doi.org/10.1016/j.conbuildmat.2020.118029
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 N. You et al. / Construction and Building Materials 242 (2020) 118029

Table 1
Chemical compositions of GGBS, FA and CS (%).

CaO SiO2 Al2O3 MgO SO3 K2O Na2O P2O5 Fe2O3 CuO LOI
GGBS 40.28 29.41 15.79 8.03 3.55 0.28 0.69 – 0.24 – 1.73
FA 6.73 53.16 27.38 1.49 0.75 1.30 0.79 0.30 5.39 – 2.71
CS 11.98 23.54 13.49 1.80 1.12 0.86 0.34 0.76 42.36 1.98 1.77

and aggregate in concrete [14]. CS powders also show good poz- Table 2
zolanic properties and are used as supplementary cementitious Main composition of FA obtained by XRD/Rietveld method (wt%).
materials [15,16]. The utilization of CS as a fine aggregate in con- Quartz Calcite Hematite Anhydrite Mullite Amorphous phases
crete is an effective way to make use of this kind of by-product. 12.78 0.52 0.73 0.55 19.10 66.32
Oluwasola et al. [17] studied the effects of using CS as fine aggre-
gate in PC mortar and concrete and pointed out that CS led to
increase in both flexural and compressive strength after 28 d of
Table 3
curing and the highest compressive strength was achieved by
Main composition of CS obtained by XRD/Rietveld method (wt%).
40% replacement of CS. Wu et al. [18] also investigated the
mechanical properties of PC concrete incorporating CS as fine Fayalite Magnetite Amorphous phases
aggregate and indicated that the strength of concrete was higher 51.31 23.84 24.85
than or showed no remarkable change compared with control
groups when the replacement of CS was less than 40%. Ayano
et al. [19] reported an increase of strength but delayed setting time Table 4
and bleeding when CS was used as fine aggregate in concrete. Basic properties of two types of fine aggregates.
Bleeding and segregation were also reported by Al-Jabri et al.
Apparent density Bulk density Tapped density Fineness
[20] and this effect can be explained by the glass-like smooth sur- (kg/m3) (kg/m3) (kg/m3) modulus
face and the low moisture absorption of CS. Sharma et al. [21] used
NS 2650 1480 1640 2.85
CS as fine aggregate in self-compacting concrete (SCC) and showed CS 3100 1720 1870 2.67
that the replacement of natural sand (NS) with CS enhanced the
fresh properties of SCC and reduced the dosage of superplasticizer.
CS was also applied to high-performance concrete (HPC) and
improved particle packing density, enhanced compressive amorphous phases. The main compositions of FA and CS are listed in Tables 2
strength, and reduced chloride ion penetration [22]. As for the uti- and 3, respectively. The main crystalline phases of CS are fayalite (Fe2SiO4) and
magnetite (Fe3O4) which is consistent with the results of other researchers [12].
lization of CS in AAMs, Mithun et al. [23] found that using CS as fine Water glass (WG) (with original modulus Ms of 3.32, SiO2 mass content of
aggregate in AAMs shows no significant change in workability but 25.81% and water content of 66.2%) and sodium hydroxide (NaOH) (analytically
reduces the total porosity, the water absorption, and the chloride pure reagent, with purity higher than 96%) were used to prepare activators.
permeability of AAMs. Mithun et al. [24] also pointed out that CS and NS were used as fine aggregate, and the basic properties of these two
types of fine aggregates are shown in Table 4. The particle size distribution of both
the replacement of NS with CS can achieve a dense and uniform
NS and CS determined according to JGJ 52-2006 [25] is presented in Fig. 1.
interfacial transition zone and results in good fatigue life of AAS
concrete.
2.2. Preparation of mortar specimens
Although there have been many studies on the use of CS as fine
aggregate in PC, only a few researchers have studied the effect of The mix proportions of the mortars were presented in Table 5. LC stands for low
CS as fine aggregate in AAMs, especially AASF materials. With the calcium group (80% FA and 20% GGBS by mass in the precursor) and HC stands for
aim of making effective use of CS to produce an environmentally high calcium group (50% FA and 50% GGBS by mass in the precursor). The alkali
friendly construction material, the workability, mechanical proper- activator was incorporated in the mixes to provide 6% Na2O by weight of precursor
and SiO2/Na2O mole ratio of 1.5 in this investigation. The liquid-to-binder mass
ties, autogenous and drying shrinkage as well as pore structure of
AASF mortars incorporating CS as partial replacement of natural
fine aggregate are studied in detail. 120
NS
2. Experimental CS
100
Cumulative pass amount (%)

2.1. Raw materials Upper boundary of

80 section II
GGBS and FA were used as precursors in this research and they were obtained
from Jiangsu Rongda new materials co. Ltd, China, and Nanjing Hongqian environ-
ment co. Ltd, China, respectively. The CS was used as fine aggregate and it was pro- 60
duced by Shijiazhuang Xinruida construction materials co. Ltd, China.
The chemical compositions of GGBS, FA and CS determined by X-ray fluores-
cence spectroscopy (ARL Perform’X 4200) are presented in Table 1. 40
The surface area of GGBS and FA measured by Blaine specific surface area tester
(FBT-9, Yichang instrument) according to ASTM C204 is 416 m2/kg and 454 m2/kg, Lower boundary of
respectively. Le Chatelier flask method was used to measure the specific gravity of 20 section II
all oven-dried powders according to ASTM C188-15. The specific gravity of GGBS
and FA is 2.90 g/cm3 and 2.47 g/cm3, respectively.
The mineral phases of raw materials (GGBS, FA and CS powder) were tested by
0
D8-Discover X-ray diffractometer (XRD) using CuKa1 radiation, 40 kV voltages and
0.075 0.15 0.3 0.6 1.18 2.36 5 10
30 mA current with the scanning step of 0.02° and the scanning speed of 0.30 step/s.
XRD/Rietveld method with 10 wt% corundum as an internal standard substance was Particle size (mm)
used to analyze the relative content of each mineral phase in GGBS, FA and CS pow-
der by XRD/Rietveld analysis software Topas. The main compositions of GGBS are Fig. 1. Particle size distribution of NS and CS.
 N. You et al. / Construction and Building Materials 242 (2020) 118029 3

Table 5
Mix proportions for AAS mortars (kg/m3).

FA GGBS Water NaOH WG NS CS

LC-0 438.4 109.6 98.8 23.6 181.9 1096.2 –
LC-20 438.4 109.6 98.8 23.6 181.9 877.0 256.5
LC-40 438.4 109.6 98.8 23.6 181.9 657.7 512.9
LC-60 438.4 109.6 98.8 23.6 181.9 438.5 769.4
HC-0 299.9 299.9 108.1 25.8 199.0 1199.6 –
HC-20 299.9 299.9 108.1 25.8 199.0 959.7 280.7
HC-40 299.9 299.9 108.1 25.8 199.0 720.0 561.3
HC-60 299.9 299.9 108.1 25.8 199.0 480.0 842.0

ratio (L/B) was 0.55. The water to binder ratio (W/B) and the binder to fine aggre- Table 6
gate ratio were 0.4 and 0.5, respectively. In this experiment, NaOH was first dis- Setting time of different pastes (min).
solved in water, then the solution was cooled to room temperature for 24 h, at
last, mixed with WG solution to get the target activator. Group Initial setting Final setting
CS was used to replace 20%, 40% and 60% volume of NS. At the same volume LC 65 105
fraction, the mass fraction of CS was higher than that of NS because of the higher HC 55 90
density of CS.

2.3. Test methods

The initial and the final setting time of pastes (as shown in Table 5 but without
fine aggregate) was tested according to Chinese Standard GB/T 1346-2011 [26]. The
fluidity of mortars was measured based on Chinese Standard GB/T 2419-2005 [27].
The rheological property of fresh mortar was evaluated by the Brookfield RS-4 rota-
tional rheometer with a paddle rotator of VT20-10.
Mortar prisms in size of 40 mm  40 mm  160 mm were demoulded after
24 h, cured in the curing room at 22 ± 2 °C and 95% RH and then used to measure
flexural strength and compressive strength at ages of 3 d, 7 d, 28 d and 56 d accord-
ing to Chinese standard GB/T 50081-2016 [28].
Autogenous shrinkage of the mortars from final setting time to 7 d after casting
was tested by the autogenous deformation tester system SBT-AS100 with a special
corrugated mould (380 mm in length and 28.5 mm in diameter) at room (20 ± 3 °C
and 55% ± 3% RH) according to ASTM C1698-09 [29].
Drying shrinkage was monitored with the mortar prisms in size of
40 mm  40 mm  160 mm with two small copper pieces at both ends from
demoulding to 210d according to Chinese standard JGJ70-2009 [30]. The mortar
was demoulded after 1 d and then kept under an indoor environment (20 °C and
55% RH). The length of mortar prisms was then measured with a micrometer caliper
from 1 d to 210 d.
The pore distribution of the mortars was measured by mercury intrusion
porosimetry (MIP) test carried out with Autopore IV9510 from Micromeritics
Instruments. The mortar samples were broken into small pieces with a hammer
and then oven-dried at 105 °C to a constant mass at 28 d before testing. The auto-
mated gas sorption analyzer (ASIQM0001-5, Quantachrome Instruments) was used
to measure the gel pores in mortar samples by N2 adsorption-desorption isotherms
(BET) method at 77 K. Mortar samples were knocked into small pieces and dried to a
constant weight with liquid nitrogen at the age of 28 d. Besides, the microstructure
of the hardened mortars after 28 d was analyzed using scanning electron micro-
scopy (FEI QUANTA 3D FEG SEM, manufactured by FEI Company) and the specimens
were dried until constant mass. The mortar samples were cut into several 10 mm
thick and coated with a thin gold layer before the SEM test.
3. Results and discussion
3.1. Setting time and fluidity
The setting time of two pastes is shown in Table 6. It can be seen
that the increase of FA in pastes prolongs both the initial and final
setting times. In the case of the mass fraction of FA at 80%, the ini-
tial and final setting times were retarded by 10 min and 15 min,
respectively compared with the group with the mass fraction of
FA at 50%. The mineralogical characterisation of FA carried out by
XRD/Rietveld has proved that it contains 33.68% of crystalline
phases including mullite and quartz, while the main phases of
GGBS are amorphous. Duxson et al. [31] reported that these crys-
talline phases make the FA difficult to be dissolved and produce
limited alkali activation products. Table 7 shows the fluidity of
mortars. It can be seen that all the LC mortars show a higher fluid-
ity compared with HC mortars regardless of the different incorpo-
ration ratios of CS. The reason for this phenomenon is that FA
Table 7
Fluidity of different mortars (mm).
Group LC-0 LC-20 LC-40 LC-60 HC-0 HC-20 HC-40 HC-60
Fluidity 285 290 295 300 260 270 280 285
particles are spherical and can have ball-bearing effects to increase
the fluidity of fresh mortars. Moreover, GGBS particles have high
amorphous phases which can have a rapid surface reaction. These
surface hydrated GGBS particles are irregular and easy to agglom-
erate [32], leading to the low fluidity of HC mortars. The incorpo-
ration of CS improves the fluidity of the mortars because of the
glazed surface and low water absorption of CS particles. But a
higher replacement rate of CS (60% volume of NS) results in a
certain extent of segregation and bleeding, as shown in Fig. 2.
However, this phenomenon is restrained in LC mortars compared
with HC mortars, because FA with the relatively large specific sur-
face area has a stronger ability to absorb water in comparison with
GGBS and hence improves the cohesiveness of the mortars [33].
3.2. Rheological performance
The AASF mortars were prepared for the rheological test and the
test program can be divided into the pre-shearing part and data-
logging part. In the first part, shear velocity was increased from 0
to 100 r/min in 30 s and decreased to 0 in 30 s. The aim of this part
was to make sure that all the groups have the same shearing state
before measuring rheological properties. After a 30 s static stop, it
came to the data-logging part. In this part, shear velocity was
increased from 0 to 150 r/min in 75 s and decreased to 0 in 75 s
as shown in Fig. 3 [34]. 150 points of data had been collected
and a typical flow curve output from the rheometer of LC-20 and
HC-20 groups was shown in Fig. 4. It was clear that these curves
had an up ramp and a down ramp, and the downward ramp did
not form a straight line as Bingham model [35]. This curve fitted
a Herschel-Bulkley model [36] (Eq. (1)).
s ¼ s0 þ Kc_ n ð1Þ
where s is shear stress (Pa), s0 is the y-intercept yield stress (Pa), K
is the consistency (Pasn), c_ is shear rate (1/s) and n is the dimen-
sionless fluidity index. Eq. (1) was used to fit the down ramp curve
and the fitting result was presented in Fig. 5.
It is obvious that all LC groups have higher yield stress and
consistency compared with HC groups. The reason for this
4 N. You et al. / Construction and Building Materials 242 (2020) 118029

Fig. 2. Segregation and bleeding of different mortars (a) LC-60, (b) HC-60.

400
150
(a) LC-20
350
125
300 Up ramp
Rotation speed/(r/min)

Shear stress/Pa

100 250

75 200
Data-logging

150 Down ramp

50
Pre-shearing
100
25
50

0
0
0 30 60 90 120 150 180 210 240
10 15 20 25 30 35
Time/s -1
Shear rate/s
Fig. 3. Program of rheological properties measurement.
400

350
(b) HC-20
phenomenon is that FA has a higher specific surface area than GGBS
and more liquid is needed to wet the surface of the precursors.
300
The effect of aggregates on the rheological characteristic (yield
stress and consistency) is accentuated in AAMs. It can be found
Shear stress/Pa

250
that the mortars with fine aggregate partly replaced by CS under
Up ramp
low substitution rate (20% and 40%) generally show higher yield 200
stress and higher consistency compared with the reference mortar
with NS. CS has a relative low fineness modulus compared with NS 150
and it means that there are higher amounts of fine powders in CS. Down ramp
Besides, the shape of CS is more irregular than NS. These properties 100

lead to high yield stress and consistency of mortars with CS,

50
according to Westerholm et al. [37]. In contrast to LC, this irregular
character of CS particles has a more significant impact on HC. But
0
when the replacement of CS is high (60%), the yield stress and con- 10 15 20 25 30 35
sistency are lower than the groups without CS. This is because CS -1
Shear rate/s
has a relatively higher density than NS and a large amount of CS
would cause the segregation and bleeding of fresh mortars and Fig. 4. The typical flow curve output from rheometer (a) LC-20, (b) HC-20.
therefore demonstrated low yield stress and consistency [22].

3.3. Mechanical properties various ages. The number (0, 20, 40 and 60) in the legend repre-
sents the replacement rate (%) of CS. All mortars show a continuous
Fig. 6 presents the flexural and the compressive strength of both increase in mechanical strength throughout 56 d. It can be easily
LC and HC mortars incorporating different levels of CS contents at found that HC group mortars have higher mechanical strength than
 N. You et al. / Construction and Building Materials 242 (2020) 118029 5

25 8 10
Yield stress
(a) LC (a) 0
Consistency coefficient

Consistency coefficient (Pa·s n)

20 20
8
6 40

Flexural strength(MPa)
60
Yield stress (Pa)

15
6
4

10
4

2
5
2

0 0
0 20 40 60 0
Replacement ratio of CS (%) LC HC LC HC LC HC LC HC
3d 7d 28d 56d
25 8
Yield stress 60
(b) HC
Consistency coefficient
Consistency coefficient (Pa·s n)
20 (b) 0
6 50 20

Compressive strength(MPa)
40
Yield stress (Pa)

15 60
40
4

10 30

2
5 20

0 0
0 20 40
Replacement ratio of CS (%)
Fig. 5. Effects of the replacement ratio of CS on the rheological properties of
different mortars: (a) LC, (b) HC.
LC group mortars, which can be explained by the higher reaction
activity of GGBS than that of FA at room temperature [38]. Ismail
et al. [39] reported that a type of calcium silicate hydrate gel incor-
porating both Na and Al (C-N-A-S-H) will be formed when the con-
tents of GGBS is higher than 50% of the total precursor, and when
the content of FA increases, the N-C-A-S-H gel will be produced.
The formation rate of N-C-A-S-H gel is lower than that of C-N-A-
S-H. Other researchers also showed that the reaction product of
GGBS is a C-A-S-H gel with a lower Ca/Si ratio and a high Al incor-
poration, while N-A-S-H gel with the three-dimensional network is
the major final product of FA [40,41]. Yang et al. [42] presented
that partial GGBS replacement of sodium alkali-activated FA mor-
tars refines the microstructure. Therefore, the distinct chemical
reaction products and optimized microstructure lead to a higher
strength of HC mortars compared with LC mortars.
From Fig. 6, replacing increased contents of NS by CS in both LC
and HC mortars has a consistent influence on the mechanical
strength in both early and later ages. A low incorporating ratio of
CS (20% and 40%) enhances both the flexural and the compressive
strength as compared to the mixes with no CS at 56 d. The reason
for this phenomenon is that the incorporation of CS improves the
fluidity of the mortars due to the glazed surface and low water
absorption of CS particles, which can contribute to more homoge-
neous and denser structure and hence to higher mechanical prop-
erties. However, when the substitute ratio of CS reaches 60%, the
mechanical strengths decline to be even lower than that of the
10
60
0
LC HC LC HC LC HC LC HC
3d 7d 28d 56d
Fig. 6. (a) Flexural strength, and (b) Compressive strength of LC and HC mortars
with different copper slag contents from 3 d to 56 d.
mortars without CS due to the inhomogeneity of the mortars
caused by segregation and bleeding as mentioned before.
3.4. Autogenous shrinkage
Fig. 7 shows the autogenous shrinkage of both LC and HC mor-
tars. It can be seen that the autogenous shrinkage of HC mortars
through 7 d is higher than that of LC mortars. It is known that auto-
genous shrinkage can be described as macroscopic volume change
caused by self-desiccation that accompanies chemical shrinkage
[43]. Chemical shrinkage results from the reduction in the absolute
volume of pastes during the reaction. According to the research of
Hojati et al. [44], lower GGBS contents of AASF paste exhibits
higher chemical shrinkage because the chemical reaction products
of FA (N-A-S-H gel) has lower molar volume than C-A-S-H gel
formed from the reaction of GGBS with alkali. However, self-
desiccation plays an important role in the autogenous shrinkage
of both LC and HC mortars. The high capillary pressure of the mor-
tars with a high content of GGBS caused by self-desiccation gives
rise to the high rate of autogenous shrinkage [45]. When the incor-
porating ratio of CS (20% and 40%) is relatively low, the autogenous
shrinkage of both LC and HC mortars shows no evident change
compared with the mortars with no CS. However, when the
6 N. You et al. / Construction and Building Materials 242 (2020) 118029

2000 20000
(a) (a)
Autogenous Shrinkage mm/mm(10 -6)

1750 17500

Drying shrinkage, εd(μstrain)

1500 15000

1250 12500
LC-0
LC-20
10000
1000 LC-40
LC-0
LC-20 7500 LC-60
750
LC-40
LC-60 5000
500
2500
250
0
0 0 20 40 60 80 100 120 140 160 180 200 220
0 1 2 3 4 5 6 7
Time (Days)
Time (Days)

20000
(b)
2000
(b) 17500
Autogenous Shrinkage mm/mm(10-6)

Drying shrinkage, εd(μstrain)

1750
15000

1500
12500

1250 10000

1000 7500 HC-0

HC-0
HC-20 HC-20
750 5000
HC-40
HC-40
HC-60 HC-60
500 2500

250 0
0 20 40 60 80 100 120 140 160 180 200 220

0 Time (Days)
0 1 2 3 4 5 6 7
Fig. 8. Drying shrinkage of (a) LC, and (b) HC mortars with different copper slag
Time (Days) contents from 1 d to 210 d.

Fig. 7. Autogenous shrinkage of (a) LC, and (b) HC mortars with different copper
slag contents.
replacement ratio of CS reaches 60%, the autogenous shrinkage sig-
nificantly increases, maybe owing to the bleeding of the mortars
with 60% CS. Bleeding usually causes a negative pressure in the
capillary water and results in high autogenous shrinkage [46].
3.5. Drying shrinkage
The plotted curves in Fig. 8 correspond to the average drying
shrinkage results of both LC and HC mortars incorporating differ-
ent levels of CS contents from 1 d to 210 d. Most of the drying
shrinkage takes place during the early ages and LC mortars show
higher drying shrinkage than that of HC mortars. Although FA in
AASF mortars increases the dimensional stability caused by the
spherical shape of FA with a micro-aggregate role to fill in the voids
and can produce more stable gels compared with GGBS [47–49],
the lower reaction activity of FA results in fewer chemical reaction
products and the looser microstructure that leads to greater drying
shrinkage [31]. The influence of CS on the drying shrinkage of AASF
mortars is also shown in Fig. 8. It is obvious that using CS to replace
NS at a low ratio (20% and 40%) reduces the drying shrinkage in
both LC and HC mortars. This effect can be explained by the
glass-like smooth surface of CS compared to NS, which can leave
more activator solution available for the chemical reaction [20].
However, high replacement of CS results in segregation and bleed-
ing, consequently increasing the drying shrinkage of AASF mortars
[47,50,51].
3.6. Pore structure
Table 8 summarizes the median pore diameter and the porosity
of both LC and HC mortars incorporating different levels of CS con-
tents at 28 d determined by MIP. It is clear that LC mortars exhibit
a higher porosity and slightly larger median pore diameter regard-
less of the replacement ratio of CS compared with corresponding
HC mortars. It is reported that the formation of the main chemical
reaction products N-A-S-H gel in alkali-activated FA experiences
slow polycondensation during the reaction process, the released
water from polycondensation can be expelled from the gel and
then form larger pores [52]. Using CS to replace NS as fine aggre-
gates in AASF mortars at a low incorporating ratio (20% and 40%)
can slightly reduce the porosity. However, a high incorporating
ratio of CS (60%) shows significantly coarser pore size distribution
compared with the mortars without CS. These results are generally
in good agreement with the workability and mechanical strength
development.
Fig. 9 presents the pore distribution of LC and HC mortars con-
taining different levels of CS as fine aggregates. The curves of all the
mortars present one-humped and concentric pore distribution
with significant porosity under 10 nm. Also, there are a little coarse
pores (>10,000 nm) related to air entrapment, indicating a compact
 N. You et al. / Construction and Building Materials 242 (2020) 118029 7

Table 8
The median pore diameter (Dmp: nm) and the porosity (%) of different mortars at 28 d.

CS replacement level (vol%) 0 20 40 60

Dmp Porosity Dmp Porosity Dmp Porosity Dmp Porosity
LC 8.7 21.30 8.4 20.88 8.2 18.39 8.1 26.18
HC 6.9 9.74 6.7 8.13 6.5 9.17 6.3 13.20

0.40 0.6
Gel Capillary Pores Macropores (a) (a) LC-0
0.35 Pores
Specific intruded Hg volume(cc/g)

0.5 LC-20
LC-0 LC-40
0.30 LC-20 3.17nm LC-60
LC-40 0.4

dV/dlog(r) (cc/g)
0.25
LC-60
0.20 0.3

0.15
0.2
0.10

0.1
0.05
6.22nm
0.00 0.0
10 100 1000 10000 100000 2 3 4 5 6 7 8 9 10
Pore size(nm) Pore size(nm)
0.25 0.6
Gel Capillary Pores Macropores (b) (b)
Pores HC-0
Specific intruded Hg volume(cc/g)

0.5 HC-20
0.20 HC-0 HC-40
HC-20 HC-60
0.4 3.97nm
HC-40
dV/dlog(r) (cc/g)

0.15 HC-60
6.22nm
0.3

0.10
0.2

0.05
0.1

0.00 0.0
10 100 1000 10000 100000 2 3 4 5 6 7 8 9 10
Pore size(nm) Pore size(nm)

Fig. 9. Pore size distribution of (a) LC, and (b) HC mortars with different copper slag Fig. 10. Log differential pore volume curve of (a) LC, and (b) HC mortars with
contents at 28 d, derived from MIP results. different copper slag contents at 28 d, derived from BET results.

structure of the mortars [53]. According to the pore size classifica-
tion proposed by Kumar et al. [54], the most probable pores in
mortars are gel pores (<10 nm) and increasing the content of GGBS
can slightly reduce the diameter of gel pores of AASF mortars.
However, it is reported that MIP cannot provide realistic results
of this range of small pore size distribution [55].
Nitrogen adsorption approach (BET) is a relatively accurate way
to detect the small pores from 0.3 to 300 nm [56] in porous mate-
rials. The density functional theory (DFT) and Monte Carlo simula-
tion methods have been applied to obtain the details of the gel
pores in this research.
Fig. 10 shows the pore size distribution of two mortars contain-
ing different amounts of CS as fine aggregates determined at 28 d
by BET. The pores analyzed here range from 2 to 10 nm using DFT.
The pore size distribution of LC mortars is a bimodal pore distribu-
tion, but a unimodal pore distribution is observed in HC mortars. In
LC mortars, the two pore diameters corresponding to the two peaks
are 3.17 nm and 6.22 nm, respectively. As for HC mortars, a broad
peak in the range from 3.97 nm to 6.22 nm is observed. The substi-
tution of FA for GGBS leads to dramatically higher porosity and the
trend presented in Fig. 10 agrees closely with the nitrogen sorption
results of Lloyd et al. [57]. This can be interpreted again by the for-
mation of C-A-S-H gels with significant bound water content in the
high content GGBS AASF mortars, while the N-A-S-H gels from the
high content FA AASF mortars are featured with a lower bound
water content [1]. It has been reported that more bound water will
provide more pore-filling capacity which results in a pore refine-
ment [4].
When CS is used to replace NS as fine aggregates in AASF mor-
tars, the gel pore content slightly increases as the amount of CS
8 N. You et al. / Construction and Building Materials 242 (2020) 118029

Fig. 11. SEM micrographs of the main chemical reaction products in different mortars (a) LC-20, (b) HC-20.

increases. The absorption capacity of CS is lower than that of NS Table 9

and provide more activator for the reaction of both GGBS and FA Composition of the main chemical reaction products in LC-20 and HC-20 mortars.
to promote the reaction degree and form more chemical reaction Atom (%) LC-20 HC-20
products. Moreover, the fine powders in CS can be activated and
Na 22.3 ± 7.3 8.1 ± 2.9
form extra chemical reaction products attributing to the amor- Mg 5.3 ± 3.9 6.9 ± 2.9
phous phases of CS [58]. Al 25.8 ± 4.5 20.7 ± 7.5
Si 42.3 ± 6.7 33.5 ± 7.8
Ca 4.3 ± 2.9 30.8 ± 5.5
3.7. SEM analysis

Fig. 11 shows SEM micrographs of both LC-20 and HC-20 mor-
tars at 28 d. The areas containing chemical reaction products were
selected and marked under SEM, and then EDX was used to analyze
the composition of different products. For the EDX test, 20 points
were randomly selected from 3 to 5 areas and the composition of
the chemical reaction products in both LC-20 and HC-20 mortars
are listed in Table 9. Although there is little difference in the mor-
phology of the two kinds of chemical reaction products, these
products present different chemical compositions. It is obvious
that the main chemical reaction products of HC mortars are cal-
cium alumina silicate hydrate (C-A-S-H) gels, whereas more
sodium alumina silicate hydrate (N-A-S-H) gels are formed in LC
mortars. These results agree with previous studies on the structure
of alkali-activated fly ash and slag blends [42,59].
4. Conclusions
The main conclusions drawn from the present investigation on
the relative performance of low calcium (LC) and high calcium (HC)
alkali-activated slag-fly ash (AASF) mortars with copper slag (CS)
as fine aggregate are summarized as follows:
LC mortars present a longer setting time, a relatively higher
fluidity, higher yield stress, and consistency compared with HC
 N. You et al. / Construction and Building Materials 242 (2020) 118029
mortars. Increasing the replacement ratio of NS with CS increases
the fluidity of AASF mortars. Increasing the incorporation ratio of
CS at lower contents (i.e. 20% and 40%) leads to increased yield
stress and consistency compared to AASF mortars without CS.
However, when the replacement of CS is high (i.e 60%), bleeding
and separation occur.
At a low incorporating ratio (i.e. 20% and 40%) inclusion of CS
results in slightly enhanced mechanical properties in both LC and
HC mortars at 56 d. However, when the incorporating ratio of CS
reaches 60% the mechanical strength reduces below that of com-
panion mortars without CS.
Compared with HC mortars, LC mortars show a relatively lower
autogenous shrinkage but higher drying shrinkage. At a low
replacement ratio (i.e. 20% and 40%) the replacement of NS with
CS in AASF mortars has little effect on autogenous shrinkage but
it reduces drying shrinkage. However, the incorporation of CS at
a high incorporation ratio (i.e. 60%) leads to increases in both auto-
genous shrinkage and drying shrinkage.
HC mortars exhibit a more refined pore structure compared to
LC mortars. The replacement of NS with CS at a suitable replace-
ment level (i.e. 20% and 40%) can reduce the total porosity, thus
improving workability, and promote the reaction degree as well
as the extra chemical reaction products that come from the activa-
tion of fine powders of CS. However, a high level of replacement
(i.e. 60%) leads to increased total porosity because of the inhomo-
geneity caused by segregation and bleeding.
Author contributions section
Nanqiao You conceived and designed the study, performed the
experiments and wrote the paper, reviewed and edited the
manuscript.
Yongchao Liu and Dawei Gu performed the experiments.
Jinlong Pan provided financial support.
Togay Ozbakkaloglu provided financial support, reviewed and
edited the manuscript.
Yamei Zhang conceived and designed the study, provided
financial support, reviewed and edited the manuscript.
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.
Acknowledgements
The authors greatly acknowledge the support provided by the
National Natural Science Foundation of China (No. 51972057 and
No. 51778132) and the International (Regional) Cooperation and
Exchange Projects, Research Fund for International Young Scien-
tists, National Natural Science Foundation of China (51650110495).
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