Construction and Building Materials 269 (2021) 121258

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Construction and Building Materials

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Effect of Na2O concentration and water/binder ratio on carbonation of

alkali-activated slag/fly ash cements
Jian Zhang a, Caijun Shi a,⇑, Zuhua Zhang a,b,⇑
a
Key Laboratory for Green & Advanced Civil Engineering Materials and Application Technology of Hunan Province, College of Civil Engineering, Hunan University, Changsha
410082, China
b
Centre for Future Materials, University of Southern Queensland, Toowoomba, QLD 4350, Australia

h i g h l i g h t s

 The effects of Na2O% and w/b ratio on the carbonation of AACs are studied.
 In carbonated AAS, CaCO3 increases when Na2O% increases from 4% to 8%.
 In AACs with 60% slag, the decreased w/b ratio improves the carbonation resistance.
 In AACs with 20% slag, the increased Na2O% reduces the carbonation degree.

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

Article history: In this study, the effects of Na2O concentration and water/binder (w/b) ratio on the phase evolution and
Received 12 June 2019 carbonation of alkali-activated slag/fly ash cements are studied. After sealed curing for 28 days, the alkali-
Received in revised form 28 September activated cement powders were performed accelerated carbonation for 7, 14, 35, 60, and 120 days, at CO2
2020
concentrations of 1.0 ± 0.2%, 20 ± 2 °C, and RH = 65 ± 2%. In alkali-activated slag at w/b ratio = 0.5, when
Accepted 5 October 2020
Available online 23 October 2020
the Na2O concentration increases from 4% to 8%, the amount of calcium carbonates after carbonation
increases due to a higher activation degree of slag and the decalcification of more C-A-S-H gels, but
the crystallinity of calcium carbonates decreases. At a fixed Na2O concentration of 6%, when the w/b ratio
Keywords:
Alkali-activated cement
decreases from 0.5 to 0.3, the formation rate of calcium carbonates and the crystallinity of calcium car-
Accelerated carbonation bonates decrease. When the content of slag is 60%, the formation rate of calcium carbonates decreases
Slag with the increased Na2O concentration from 6% to 8%, due to the higher reaction degree of fly ash and
Fly ash the formation of more N-A-S-H gels; and the amount of calcium carbonates increases with the decreased
Na2O concentration w/b ratio. When the content of slag is 20%, the increased Na2O concentration could decrease the forma-
Water/binder ratio tion rate of calcium carbonates significantly, but the effect of the w/b ratio is limited.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction excellent mechanical properties while require relatively low acti-

Alkali-activated cements (AACs), prepared with aluminosili-
cates and alkaline activators, have been studied extensively, based
on the economic and environmental concerns [1–6]. Ground gran-
ulated blast furnace slag and fly ash are the major aluminosilicates
used as precursors in today’s commercial AAC concretes [7]. Fly
ash-based AACs (geopolymers), in which N-A-S-H gels with the
pseudo-zeolitic structure are the main products, usually require
higher alkali dosage and elevated curing temperature to achieve
useful strength for construction purposes [4]. Slag-based AACs,
dominated by C-A-S-H gels with tobermorite-like structure, have
⇑ Corresponding authors.
E-mail addresses: cshi@hnu.edu.cn (C. Shi), Zuhuazhang@hnu.edu.cn (Z. Zhang).
vator dosage under ambient conditions [8], but some practical
challenges are needed to overcome, such as fast setting [9] and
large shrinkage [10]. Therefore, the alkali-activated slag/fly ash
cements are of interest, because the combination of the reaction
products exhibits improved properties and durability when com-
pared to binders prepared with a sole raw material [9,11–13].
Although AACs have shown satisfactory performances in some
applications [8], the durability is still an unproven issue [14]. For
example, in terms of carbonation, the dissolved CO2 in pore solu-
tion could react with reaction products in AACs, reducing the pH
of pore solution and increasing the corrosion risk [15]. The carbon-
ation rate of AACs is mainly determined by the physical properties
of the matrix, in particular porosity and permeability, and also by
cement chemistry including its susceptibility to decalcification

https://doi.org/10.1016/j.conbuildmat.2020.121258
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
J. Zhang, C. Shi and Z. Zhang
[16]. In alkali-activated slag/fly ash cements, the carbonation
mechanism of individual gel is similar to that prepared with a sin-
gle component. Bernal et al. [17] found that the decalcification of
C-A-S-H in alkali-activated slag (AAS) can make a large degree of
changes in the gel structure; while the N-A-S-H gel of alkali-
activated fly ash is more porous and is ready to be carbonized,
but the gel structure seems essentially unchanged after
carbonation.
Some literatures have summarized the influence factors of car-
bonation in AACs [18,19], including precursors, activators, CO2 con-
centration, relative humidity (RH), and so on. The rates of pore
solution carbonation and gel carbonation seem to be particularly
distinct from each other at higher CO2 concentrations [20], mean-
ing that such test conditions may lead to a misleading prediction of
the performance of AACs. Byfors and Bakharev et al. [21–23] found
that the carbonation rate of AAS was much faster than PC as eval-
uated by accelerated carbonation tests, while the natural carbona-
tion rate of AAS is close to PC [23,24]. The accelerated carbonation
test at CO2 concentration higher than 1% is difficult to represent
the carbonation behavior in the natural environment for alkali-
activated slag [25], due to the changed balance of alkali carbonate
phases with increasing CO2 concentration [26].
However, little attention is paid to the effects of Na2O concen-
tration of activators and water/binder (w/b) ratio on the carbona-
tion mechanisms of AACs. The Na2O concentration means Na2O
content of activators with respect to the mass of precursors (slag
and fly ash in this study) in AACs. Although alkali in AACs is mainly
used for the dissolution of slag and fly ash, the alkalinity of pore
solution is highly important as a main buffer during carbonation.
It was reported that the carbonation depth of AACs decreased with
the increased Na2O concentration from 3 to 7% [27–29], as the
increased Na2O concentration leads to more C-A-S-H gels enriched
in Na+ and the N-C-S-H formed presents a reduced susceptibility to
carbonation [30,31]. Besides the higher alkalinity of pore solution
and reaction degree of slag, Shi et al. [32] found that the increased
carbonation resistance of AAS mortars is attributed to the lower
porosity and smaller average pore size with increased alkalinity,
which could inhibit the CO2 diffusion and reduce the carbonation
rate.
For OPC concretes, the water/cement ratio is the most reliable
parameter in predicting the carbonation resistance [33,34]. How-
ever, in AACs, the water plays important roles during dissolution,
polycondensation, and geopolymerization [35–37], which is differ-
ent from that for OPC. Bernal et al. [38] found that the water con-
tent of AAS cements has a significant effect on the reaction kinetics
and the structure of reaction products, which could affect the car-
bonation behaviors.
The purpose of this study is to investigate the phase evolution
and carbonation of alkali-activated slag/fly ash cements with dif-
ferent Na2O concentrations and w/b ratios. Via X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (FTIR), and thermo-
gravimetry/differential thermograms (TG/DTG), reaction mecha-
nisms are examined and compared. The findings of this study
can improve the understanding of carbonation mechanisms of
AACs, which is beneficial to the establishment of prediction models
of carbonation and the future industrial application.
2. Experimental program
2.1. Materials
Ground granulated blast furnace slag and Class F fly ash were
used as the raw materials for the production of AACs. The chemical
compositions of slag and fly ash are shown in Table 1. The main
crystalline phases in fly ash are quartz (SiO2, PDF# 00-046-1045),
2
Construction and Building Materials 269 (2021) 121258
mullite (PDF# 01–083-1881), and hematite (Fe2O3, PDF# 01-085-
0599), while the slag is mainly amorphous, as showed in Fig. 1.
The particle size distribution of these materials is displayed in
Fig. 2. The slag has a specific gravity of 2.9, Blaine fineness of
390 m2/kg, and d50 of 16.6 lm. The fly ash has a specific gravity
of 2.35, Blaine fineness of 370 m2/kg, and d50 of 23.8 lm.
The alkaline solution was formulated by mixing a commercial
sodium silicate solution (28.5 wt% SiO2, 9.5 wt% Na2O and
62.0 wt% H2O) and solid sodium hydroxide pellets, to reach a mod-
ulus of 1.5. The quantity of activator used in each mixture was
designed to be 4, 6, and 8 wt% Na2O with respect to the mass of
precursors. Water was added to the activation solution to reach a
water/binder ratio of 0.3 and 0.5, here is the total water/
(slag + fly ash + anhydrous activator). The activator solution was
allowed to cool to room temperature prior to prepare of specimens.
The mixture formula of AACs was produced as shown in Table 2.
2.2. Sample preparation
After casting in polypropylene bottle mold of size U
60  100 mm, the pastes were subjected to the continuous rotation
for 24 h to prevent significant segregation, then cured within the
bottle under standard curing condition (20 ± 2 °C, RH  95%). After
curing for 28 days, the paste cylinders were cut by 20 mm from
both ends to remove the outer layers to avoid possible early car-
bonation. The remaining part was cracked and ground into fine
powder to pass a 74 lm sieve for accelerated carbonation test.
Uncarbonated finely ground powders were used for reference
samples.
2.3. Testing methods
2.3.1. Carbonation tests
The powder samples were placed in a humidity and CO2-
controlled testing chamber to perform accelerated carbonation at
CO2 concentrations of 1.0 ± 0.2%, 20 ± 2 °C, and RH = 65 ± 2%. Spec-
imens were removed from the chamber after 7, 14, 35, 60, and
120 days of exposure, marked as C7, C14, C35, C60, and C120,
respectively. Anhydrous ethanol was used to stops reactions of car-
bonated and uncarbonated powders. These samples were stored in
a vacuum chamber without CO2.
2.3.2. Xrd
XRD analysis was performed to analyze the mineral composi-
tion of uncarbonated samples. The powders were dried in an oven
at 50 °C for 24 h, then ground by agate mortar and sieved through a
20 lm sieve to keep the fineness as uniform as possible. The fine
powders were analyzed using the Rigaku X-ray diffractometer with
Cu Ka radiation. The samples were scanned from 5 to 65° (2h) at a
rate of 30 s/° (with a step of 0.02°).
2.3.3. Ftir
The FTIR was conducted using a Thermo-Scientific IS10 FTIR
workstation and employing the KBr disc method. Each sample
was tested at a resolution of 2 cm 1 with 32 scans. The relative
absorbance spectra over the range of 1300–800 cm 1 were sub-
jected to a deconvolution analysis using the Peakfit software with
Gaussian peak shape and variable full width at half maximum
(FWHM). The reliability of the deconvolution was controlled by
minimizing the component band number and maintaining the
regression coefficient (r2) above 0.99.
2.3.4. Tg/Dtg
The samples in powder form were heated from 30 to 1000 °C in
a nitrogen atmosphere at a rate of 10 °C/min in the TGA instrument
(Netzsch STA 409PC).
J. Zhang, C. Shi and Z. Zhang Construction and Building Materials 269 (2021) 121258

Table 1
Chemical analysis by XRF of raw materials, mass %. LOI is the loss on ignition at 1000 °C.

CaO SiO2 Al2O3 MgO Fe2O3 Na2O K2O TiO2 SO3 LOI
Slag 38.81 33.81 14.78 7.09 0.36 0.26 0.44 0.52 2.49 1.40
Fly ash 1.32 52.64 34.11 0.5 3.25 0.52 1.56 1.72 0.41 3.29

3. Results and discussion

3.1. Uncarbonated AACs

3.1.1. XRD analysis

Fig. 1. XRD diffractograms of raw slag and fly ash.
Fig. 2. The particle size distribution of raw slag and fly ash.
Table 2
Mix proportions of the alkali-activated cements.
Fig. 3 illustrates the XRD diffractograms of uncarbonated alkali-
activated slag/fly ash cements after curing for 28 days. In alkali-
activated slag, the main reaction products, C-A-S-H gel (similar
to tobermorite, Ca5(Si6O16)(OH)2, PDF# 01–089-6458) between
25 and 35° 2h, and hydrotalcite (Mg6Al2(CO3)(OH)16
4H2O, PDF#
00–014-0191) are observed. When the content of slag is 60%, mul-
lite, quartz, and hematite, which remain unaltered after activation
of fly ash [39], are detected in blended cements. When the content
of slag is 20%, the broad feature at 15-35° 2h is mainly attributing
to the N-A-S-H gel, which is difficult to analyze with XRD [40]; and
hydrotalcite cannot be found.
As shown in Fig. 3 (a), it can be seen that the Na2O concentra-
tion has little effect on the type of reaction products in AACs. It
was investigated that an increased Na2O concentration (4–8%)
could accelerate the reaction kinetics [41] and increase the volume
proportion of crystalline reaction products, higher Na2O concentra-
tion leads to a higher degree of reaction and more C-(N-)A-S-H
[42,43]; but had little influence on the type of reaction products
[43]. An increase in the alkaline solution/binder ratio favors the
formation of zeolites and N-A-S-H gels [40], but it is not evident
here, indicating that the Na2O concentration used (6–8% Na2O) is
moderate. In addition, the Na2O concentration has little effect on
the formation of hydrotalcite phases. The higher initial pH could
favor the degree of hydrotalcite formation [44], while the available
free silica in solution is thought to enhance the incorporation of Al
in C-A-S-H/N-A-S-H gels during the initial reaction stage, inhibiting
the formation of hydrotalcite.
As shown in Fig. 3 (b), when the w/b ratio increases from 0.3 to
0.5, the C-A-S-H phases become slightly more intense and nar-
rower, which could reflect a higher degree of structural ordering
in the C-A-S-H. In the study of Bernal et al. [38], they found that
the peak of C-A-S-H in AAS mortars after curing for 56 days
becomes less intense and broader with the increased w/b ratio
from 0.40 to 0.48. The conflicting conclusion might be related to
the different curing periods and the different range of w/b ratio
used. In addition, Ismail et al. [45] found that the intensity of C-
A-S-H in alkali-activated slag/fly ash pastes decreased with
increasing w/b ratio from 0.40 to 0.60, while the ‘binder’ in w/b
ratios was defined as the fly ash and slag content in their study,
then the addition of water reduced the alkalinity of activators
and thus influences the reaction development.

Mix denote Slag/fly ash Na2O concentration Water/binder 3.1.2. FTIR analysis
ratio (wt.%) ratio FTIR is powerful in determining the structure of the functional
S100N4 100/0 4 0.5 groups that build up the molecules. It enables the characterization
S100N6/S100W0.5 100/0 6 0.5 of the Si–O–T (T: tetrahedral Si or Al) symmetric and asymmetric
S100N8 100/0 8 0.5 bonds, which is useful to track the changes in gel structures as a
S60N6/S60W0.5 60/40 6 0.5
S60N8 60/40 8 0.5
function of various factors. The standardized area percentages of
S20N6/S20W0.5 20/80 6 0.5 the deconvoluted FTIR spectra were used to quantify the reaction
S20N8 20/80 8 0.5 products in many studies [46–48]. It was considered that the FTIR
S100W0.3 100/0 6 0.3 spectra and self-deconvolution can provide reliable indicators of
S60W0.3 60/40 6 0.3
the changes in reaction sequence, product formation, and the
S20W0.3 20/80 6 0.3
chemical arrangement in AACs [49].
3
J. Zhang, C. Shi and Z. Zhang Construction and Building Materials 269 (2021) 121258

Fig. 3. XRD diffractograms of uncarbonated AACs with different (a) Na2O concentrations and (b) w/b ratios.

Fig. 4. FTIR spectra of (a) raw slag and fly ash, deconvolution results of (b) slag and (c) fly ash.

4
J. Zhang, C. Shi and Z. Zhang
Fig. 4 shows the infrared spectra of the unreacted slag and fly
ash in the range of 2000–400 cm 1. In Fig. 4 (a), the small vibration
band observed at 1640 cm 1 corresponds to the bending vibration
modes of H–OH bonds and the band between 1200 and 950 cm 1 is
associated with the asymmetric stretching vibration mode of Si–
O–T bonds. This band is centered at 993 cm 1 in slag and
1091 cm 1 in fly ash, consistent with the differences in the chem-
ical composition and glass structures of these materials. Trace car-
bonates are identified in unreacted slag, associated with the CO2– 3
out-of-plane bending mode at 875 cm 1 [50]. In the spectrum of
fly ash, the signal at 555 cm 1 is associated with the octahedrally
coordinated aluminum in mullite [39].
Fig. 4 (b) shows the deconvolved bands in the spectra of the raw
slag powder using the Gaussian curve functions. The dominant
band at 986 cm 1 represents the asymmetric stretching vibration
of Si–O–T bond, as previously mentioned. This band peak is at a
slightly lower frequency than the value assigned to the gel compo-
nent in the original spectrum, which is closely related to the math-
ematical processing of band deconvolution and spectrum
subtraction [51]. The absorption bands at approximately 1200,
1100, 950, 900, and 850 cm 1 are associated with the Si–O–Si
stretching vibrations of the SiQn units for n = 4, 3, 2, 1, and 0,
respectively [52]. Then the bands at 900 and 850 cm 1 can be
attributed to Q1 and Q0, respectively. Fig. 4 (c) shows the infrared
spectroscopic results for the original fly ash. The components
appearing at 1011, 1081, and 1183 cm 1 are attributed, respec-
tively, to the vitreous phase of the fly ash, quartz, and mullite
[51]; while the component at 1136 cm 1 is associated with both
quartz and mullite.
The FTIR spectra of uncarbonated AACs in the range of 2000–
400 cm 1 are presented in Fig. 5. The bending vibration modes of
H–OH bonds at 1640 cm 1 are related to the chemically bound
water in hydrated products [53]. The asymmetric C O stretching
bands of CaCO3 polymorphs at 1500–1400 cm 1 and the out-of-
plane C O bending modes at 875 cm 1 are related to the weath-
ering of raw materials or the natural carbonation during the sam-
ple preparation. The signal at 555 cm 1 is associated with the
octahedrally coordinated Al in mullite [39], which is detected in
unreacted fly ash too.
In alkali-activated slag, the band at 991 cm 1 in S100N4 is
assigned to the asymmetric stretching vibration of Si–O–T bonds
in C-A-S-H gels. The variation of this band with the increase of
Na2O concentration from 4% to 8% is not evident as shown in
Fig. 5 (a), thus a further study by the deconvoluted FTIR spectra
Fig. 5. FTIR spectra of uncarbonated AACs with different (a) Na2O concentrations and (b) w/b ratios.
5
Construction and Building Materials 269 (2021) 121258
was conducted. With the incorporation of fly ash, this Si–O–T band
between 1200 and 950 cm 1 shifts to higher wavenumber, indicat-
ing the formation of gel with a higher polymerization degree of Si
[54]. When the content of slag is 60%, this wavenumber of main Si–
O–T increases from 986 to 998 cm 1 as the increased Na2O concen-
tration from 6% to 8%, may be related to a higher degree of reaction
of fly ash or more Si from the activator [42,55].
The FTIR spectra of uncarbonated AACs with different w/b ratios
in the range of 2000–400 cm 1 are presented in Fig. 5 (b). When
the content of slag  60%, the wavenumbers of Si–O–T in AACs
with the w/b ratio of 0.3 are higher than 0.5. Different to those
high-Ca AACs, the wavenumber of Si–O–T of S20W0.5
(1008 cm 1) is higher than that of S20W0.3 (991 cm 1), indicating
that the degree of polymerization is higher when the w/b ratio is
0.5. However, Ismail et al. [45] found that the effect of w/b ratio
of 0.40–0.60 on the gel nanostructure of AACs (slag/fly ash
ratio = 50/50) is rather limited by the FTIR spectra. Therefore, more
exact information is needed by the spectra deconvolution study.
The deconvoluted spectra between 1300 and 800 cm 1 for
uncarbonated AACs are shown in Fig. 6. The signal at 865 cm 1 is
assigned to the Si–O terminal vibrations [51], the band at
962 cm 1 corresponds to the Si–O stretching in Si–O–Na structures
[47]. The band at 1032 cm 1 is attributing to the binding of sodium
onto a silicate-based gel [56]. In S100N4, the main band at
983 cm 1 is assigned to the Si–O stretching vibrations at Q2 sites,
and the bands at 1088 cm 1 and 1136 cm 1 are due to typical
bands of Q3 and Q4 sites, respectively [48].
As shown in Fig. 6 (a)-(c), with the increase of Na2O concentra-
tion from 4% to 8%, the wavenumber of the main band increases
slightly from 983 to 986 cm 1, accompanied by the increase of rel-
ative area from 53.1% to 62.5%, due to a higher reaction degree.
Compared to the variation of wavenumbers, the variation of rela-
tive areas of deconvoluted peaks is more reliable to evaluate the
phase evolution of AAS. Zuo et al. [43] also found that the amount
of C-(N-)A-S-H in AAS increased with the increase of Na2O content
from 4% to 8%. In the study of Shi et al. [32], no shift of wavenum-
bers was observed in AAS when the alkali dosage changed from 6%
to 8%. In this study, the effect of Na2O concentration on the phase
evolution of AAS is not evident when the Na2O concentration
increases from 6% to 8%, with the relative area of C-A-S-H at Q2
sites increases from 59.0% to 62.5%; thus, the effect is more evident
when the Na2O concentration changes from 4% to 6%. With the
incorporation of fly ash, the wavenumber of the C-A-S-H at Q2 sites
increases slightly with the increase of Na2O concentration from 6%
J. Zhang, C. Shi and Z. Zhang
to 8%, accompanied by the increase of relative areas. In addition,
the relative areas of Q4 at 1136 and 1183 cm 1 increase with the
increase of Na2O concentration, indicating that more Na2O is ben-
eficial to the reaction of fly ash in AACs.
As shown in Fig. 6 (b) and (d), when the w/b ratio reduces from
0.5 to 0.3, the wavenumber of the C-A-S-H in AAS slightly increases
from 984 to 987 cm 1, accompanied by the increase of relative area
from 59.0% to 62.2%, due to a higher reaction degree of slag and fly
ash. Based on the XRD result, it can be concluded that the C-A-S-H
phases in AAS have a lower degree of structural ordering but their
quantity increases when the w/b ratio is 0.3. Additionally, the rel-
ative areas of bands at 962 and 1032 cm 1 are lower in S100W0.3,
while the relative areas of bands at 1088 and 1136 cm 1 are higher,
compared to S100W0.5. When the content of slag is 60%, a similar
result about the variation of C-A-S-H gels is obtained. When the
content of slag is 20%, although the wavenumber of Q2 decreases
from 1000 to 991 cm 1 with the w/b ratio decreases from 0.5 to
0.3, the relative area increases from 54.9% to 58.1%. It indicates that
the decrease of w/b ratio from 0.5 to 0.3 is beneficial to the increase
of reaction degree of slag and fly ash in AACs, and the more C-A-S-
H gels generate due to the activation of slag.
Fig. 6. Deconvolution spectra of (a) S100N4, (b) S100N6/S100W0.5, (c) S100N8, (d) S100W0.3, (e) S60N6/S60W0.5, (f) S60N8, (g) S60W0.3, (h) S20N6/S20W0.5, (i) S20N8, (j)
S20W0.3.
6
Construction and Building Materials 269 (2021) 121258
The deconvoluted FTIR spectra are useful in the understanding
of the changes in reaction mechanisms and product formation,
which are important to study the effect of Na2O concentration
and w/b ratio on the carbonation of AACs.
3.1.3. DTG analysis
DTG results of uncarbonated alkali-activated cements are
shown in Fig. 7. The mass loss between 30 and 105 °C is defined
as the loss of free and loosely bound water [43]. When the content
of slag is  60%, the broad endothermic peaks at 330–400 °C are
mainly attributed to the hydrotalcite-type phases [17,57,58],
agrees with the XRD analysis. With the incorporation of fly ash, this
peak shifts to higher temperatures slightly with the increase of
Na2O concentration from 6% to 8%, due to a higher reaction degree.
As the Na2O concentration of sodium silicate activators has little
effect on the type of reaction products based on the XRD results
and previous studies [38,43]. In Fig. 7 (b), the endothermic peaks
at 90–120 °C shift to higher temperatures when the w/b ratio
decreases from 0.5 to 0.3, as the C-A-S-H phases in AACs have a
lower degree of structural ordering but the higher extent of forma-
tion when the w/b ratio is 0.3.
J. Zhang, C. Shi and Z. Zhang Construction and Building Materials 269 (2021) 121258

Fig. 6 (continued)

3.2. Carbonated AACs 400 cm 1 for alkali-activated slag cements after carbonation
are presented in Fig. 8. The changes in polymerization degree
3.2.1. The effect of Na2O concentration of main products and calcium carbonate polymorphs during car-
3.2.1.1. FTIR analysis. The FTIR spectra in the range of 2000– bonation can be obtained by the FTIR spectra. In S100N4, the

7
J. Zhang, C. Shi and Z. Zhang Construction and Building Materials 269 (2021) 121258

Fig. 7. DTG of uncarbonated AACs with different (a) Na2O concentrations and (b) w/b ratios.

Fig. 8. FTIR spectra of carbonated alkali-activated slag cements with different Na2O concentrations, (a) S100N4, (b) S100N6, (c) S100N8.

8
J. Zhang, C. Shi and Z. Zhang
wavenumber of the main Si–O–T vibration bands at 991 cm 1
shifts to 1027 cm 1 after carbonation of 120 days. This is due
to the decalcification of C-A-S-H gels and the formation of a
higher degree of polymerization of silicates [32]. The difference
of the shift is little when the Na2O concentration increases from
4% to 8%, considering the results of deconvoluted FTIR spectra.
The variation of the main Si–O–T vibration bands occurs mainly
before 60 days for all three AAS samples, indicating the carbon-
ation occurs mainly before 60 days given that the magnitude of
the silicate band shift is indicative of the polymerization degree
[59].
The relative areas of bands at 875 cm 1 (calcite, aragonite, and
vaterite) [50,60] and bands at 713 cm 1 (calcite and aragonite)
increase along with carbonation time, suggesting that the decalci-
fication of C-A-S-H gels results in the formation of calcium carbon-
ates. The bands at 1500–1400 cm 1 attributing to the asymmetric
C O stretching bands of CaCO3 polymorphs are used to evaluate
the carbonation products. In S100N4, from 7 to 60 days, the bands
at 1454 cm 1 attributing to vaterite and aragonite [61] are
detected. And this band shifts to 1430 cm 1 of calcite and aragonite
[50] after 120 days, suggesting a substantial CaCO3 formed. When
the Na2O concentration increases to 6%, the asymmetric C O carbonates might be decreased when the Na2O concentration
stretching bands at 1418 cm 1 (calcite and vaterite) are found from
Fig. 9. FTIR spectra of carbonated alkali-activated blended cements with different Na2O concentrations, (a) S60N6, (b) S60N8, (c) S20N6, (d) S20N8.
9
Construction and Building Materials 269 (2021) 121258
7 to 60 days and increase to 1438 cm 1 (calcite and vaterite) after
120 days. When the Na2O concentration increases to 8%, the bands
at 1420 cm 1 during 35–60 days are related to calcite and vaterite,
and the bands of 1445 and 1450 cm 1 are assigned to vaterite.
After 120 days, the band at 1435 cm 1 is assigned to calcite, indi-
cating a more stable CaCO3 formed.
The FTIR spectra in the range of 2000–400 cm 1 for alkali-
activated slag/fly ash blended cements with different Na2O concen-
trations after carbonation are shown in Fig. 9. When the content of
slag is 60%, in S60N6, the asymmetric C O stretching bands at
1454 cm 1 attributing to vaterite and aragonite [61] are detected
during carbonation. The band at 1418 cm 1 increases to
1438 cm 1 during 60 and 120 days, suggesting a substantial CaCO3
formed. In S60N8, the band at 1418 cm 1 increases to 1423 and
1435 cm 1 (calcite) after 35 days, indicating a faster conversion
rate of metastable calcium carbonates to calcite occurs when the
Na2O concentration is higher. Moreover, the shift of the main Si–
O vibration band in S60N8 (998 ? 1023 cm 1) is smaller than that
in S60N6 (986 ? 1029 cm 1) after carbonation, and the variation
of the shift mainly occurs before 35 days when the Na2O
concentration is 6%. It indicates that the formation rate of calcium
increases from 6% to 8%.
J. Zhang, C. Shi and Z. Zhang
When the content of slag is 20%, in S20N6, the asymmetric C O
stretching bands at 1435 cm 1 and 1446 cm 1 (calcite and vaterite,
respectively) shift to 1418 cm 1 (calcite and vaterite) after 35 days,
indicating the continuous carbonation. After 60 days, this band
shifts to 1429 cm 1 (calcite and aragonite), due to the transforma-
tion of calcium carbonate polymorphs. Similarly, in S20N8, the band
at 1420 cm 1 (calcite and vaterite) shifts to 1430 cm 1 (calcite and
aragonite) after 60 days. The shift of the main Si–O vibration band
in S20N8 (1011 ? 1023 cm 1) is slightly smaller than that in
S20N6 (1008 ? 1026 cm 1), and the variation of the shift mainly
occurs before 35 days when the Na2O concentration is 6%.
3.2.1.2. TG/DTG analysis. The DTG data for AACs with different Na2O
concentrations after carbonation is shown in Fig. 10. The broad
endothermic temperature ranges from 400 to 800 °C is attributing
to the decomposition of calcium carbonate phases [32,62]. In
S100N4, this peak of calcium carbonates shifts from 538 to
568 °C during 14–35 days, accompanied by the presence of a peak
at 653 °C. According to the results of FTIR, this transformation of
calcium carbonate polymorphs may be related to the generation
of aragonite. After 120 days, the peaks of calcium carbonates shift
to 700 °C and become more intense. This is due to the thermal
decomposition of calcite [17], which is formed by the transforma-
Fig. 10. DTG of carbonated alkali-activated cements, (a) S100N4, (b) S100N6, (c) S100N8, (d) S60N6, (e) S60N8, (f) S20N6, (g) S20N8.
10
Construction and Building Materials 269 (2021) 121258
tion of metastable calcium carbonates [63]. When the Na2O con-
centration increases, the conversion rate of calcium carbonate
polymorphs decreases, and the decomposition peaks of calcium
carbonates are at ~ 530 °C during 14–60 days. Therefore, it is
believed that the conversion rate of calcium carbonates into a more
stable form is faster, and the crystallinity of calcium carbonates
formed during carbonation is higher when the Na2O concentration
is 4%. Although the Na2O concentration of activators has little
effect on the type of reaction products in AAS cements based on
the XRD results, the gel structures of C-A-S-H formed might be dif-
ferent, and more advanced characterization techniques are needed
to understand this difference. Nevertheless, it can be determined
that the effect of Na2O concentration on the phase evolution and
carbonation of AAS is more evident when the Na2O concentration
increases from 4% to 6%.
When the content of slag is 60%, the effect of Na2O concentra-
tion (6–8%) on the conversion rate of calcium carbonates and crys-
tallinity of calcium carbonates is little. In the study of Nedeljković
et al. [31], they investigated that alkalis play a less important role
in carbonation resistance when the AACs are rich in slag.
And the identified CaCO3 is mainly crystalline in AAS paste after
180 days of carbonation, while it is mainly amorphous in other
alkali-activated pastes with the incorporation of fly ash [59]. When
J. Zhang, C. Shi and Z. Zhang
Fig. 10 (continued)
the content of slag is 20%, the DTG of carbonated low-Ca AACs is
different from that of high-Ca AACs, especially the decomposition
temperatures of calcium carbonates. In S20N6, the peaks of CaCO3
are centered at 600–700 °C during 7–60 days, then shift to ~ 674 °C
after 120 days, with the increased intensity. And the formation rate
of calcium carbonates decreases at an early stage when the Na2O
concentration increases to 8%.
Fig. 11 (a) is the schematic diagram of mass loss in S100N6 after
the carbonation of 14 and 120 days from the TG. The mass loss
between 30 and 105 °C is defined as the loss of free and loosely
bound water in AACs, and the broad temperature ranges from
400 to 800 °C attributed to the variation of crystallinity of CaCO3
is proposed to evaluate the CO2 uptake in AACs, corresponding to
the works of literature [32,62]. The quantification of the CO2 bind-
ing capacity of reinforced concrete is of high importance for pre-
dicting the carbonation potential and service life of concrete
structures.
The calculated content of calcium carbonates due to carbona-
tion in AACs and fitting curves (exponential function, y = y0 + A
e(-
x/t)
) are shown in Fig. 11 (b). In alkali-activated slag, the amount of
calcium carbonates increases with the increase of Na2O concentra-
tion from 4% to 8%, especially when the Na2O concentration
11
Construction and Building Materials 269 (2021) 121258
increases from 4% to 6%. As the higher Na2O concentration leads
to a higher degree of reaction and more C-A-S-H gels, and the effect
is more evident when the Na2O concentration increases from 4% to
6%. The carbonation mainly occurs before 60 days, corresponding
to the FTIR results. Song et al. [28] also found that the amount of
C-A-S-H increased and the carbonation resistance improved by
increasing the Na2O concentration from 3% to 7% in AAS mortars.
When the content of slag is 60%, the carbonation mainly occurs
before 35 days in S60N6. When the Na2O concentration increases
to 8%, the formation rate of calcium carbonates decreases but the
amount of calcium carbonates changes little, may be related to a
higher degree of reaction of fly ash and more N-A-S-H gels formed
with a higher Na2O concentration. And the amount of CaCO3 after
carbonation of 120 days is lower than that in AAS powders. When
the content of slag is 20%, a similar phenomenon is observed.
Therefore, the increase of Na2O concentration from 6 to 8% could
improve the carbonation resistance of AACs effectively. However,
Nedeljković et al. [59] found that the alkali-activated pastes have
similar CO2 binding capacity regardless of the fly ash/slag ratio,
and the silicate functional groups corresponding to the reaction
products in the pastes were progressively changing during the first
7 days, after which only carbonate groups changed.
J. Zhang, C. Shi and Z. Zhang
Fig. 11. (a) Schematic diagram of mass loss and (b) calculated content of calcium carbonates and fitting curves in carbonated AACs with different Na2O concentration.
3.2.2. The effect of water/binder ratio
3.2.2.1. FTIR analysis. The FTIR spectra in the range of 2000–
400 cm 1 for carbonated AACs with different w/b ratios are pre-
sented in Fig. 12. The relative areas of bands at 875 cm 1 and
713 cm 1 increase with the increased carbonation time, indepen-
dent of the w/b ratio, due to the formation of calcium carbonates.
In S100W0.3, the wavenumber of the main Si–O–T vibration bands
at 993 cm 1 shifts to 1022 cm 1 after carbonation of 120 days, and
the variation of the main Si–O–T bands mainly occurs before
60 days. From 7 to 35 days, the band at 1418 cm 1 attributing to
calcite and vaterite [50] is detected. After 60 days, this band shifts
to 1435 cm 1 (calcite); and after 120 days, the band at 1430 cm 1
is assigned to calcite and aragonite. Therefore, the conversion rate
of calcium carbonates from metastable to more stabilized is faster
when the w/b ratio is 0.3.
When the content of slag is 60%, the variation of S60W0.3 after
carbonation is similar to S100W0.3, and the conversion rate of
calcium carbonates is faster when the w/b ratio is 0.3. When the
content of slag is 20%, the carbonation behavior of S20W0.3 is sim-
ilar to that of S20W0.5, and the carbonation mainly occurs before
35 days.
3.2.2.2. TG/DTG analysis. The DTG data for carbonated alkali-
activated cements with different w/b ratios are shown in Fig. 13.
In S100W0.3, the mass loss peaks of calcium carbonates are mainly
distributed at ~ 480 °C during 14–35 days, with a small peak
at ~ 640 °C. After 60 days, the endothermic peaks of calcium car-
bonates shift to ~ 690 °C (calcite) and become more intense, indi-
cating the substantial formation and transformation of calcium
carbonate polymorphs. When the w/b ratio of AAS increases to
0.5, the conversion rate of calcium carbonates decreases, but the
crystallinity of calcium carbonates becomes higher at the early
stages. It might be related to the carbonation of more crystalline
products and the C-A-S-H with a higher degree of structural
ordering.
When the content of slag is 60%, the DTG of S60W0.3 after car-
bonation is similar to S100W0.3, and the conversion rate of cal-
cium carbonates is faster when the w/b ratio is 0.3. When the
content of slag is 20%, the DTG of low-Ca systems after carbona-
tion is different from that of high-Ca systems. The DTG of
S20W0.3 is similar to that of S20W0.5, but the endothermic peak
of calcium carbonates is slightly more intense when the w/b ratio
is 0.3.
12
Construction and Building Materials 269 (2021) 121258
The calculated contents of calcium carbonates and fitting curves
of AACs with different w/b ratios are shown in Fig. 14. In AAS pow-
der samples, the formation rate of calcium carbonates of S100W0.3
is slower than that of S100W0.5 at an early stage, and the carbon-
ation mainly occurs before 60 days when the w/b ratio is 0.3. How-
ever, the amount of calcium carbonates after 120 days is similar
between S100W0.3 and S100W0.5, although there is still a growing
trend in S100W0.3. According to the XRD and FTIR results, a lower
degree of structural ordering but a higher amount of C-A-S-H are
detected when the w/b ratio reduces from 0.5 to 0.3.
When the content of slag is 60%, the reduced w/b ratio also
decreases the formation rate of calcium carbonates, while the
amount of calcium carbonates in S60W0.3 after 120 days is signif-
icantly higher than that in S60W0.5. It can be concluded that in
high-Ca systems (100% and 60% slag), the reduced w/b ratio could
decrease the formation rate of calcium carbonates while increasing
the amount of calcium carbonates. When the content of slag is 20%,
the main carbonation occurs before 35 days. The amount of cal-
cium carbonates of carbonated S20W0.3 is higher than that of
S20W0.5, indicating a higher carbonation degree in S20W0.3.
4. Conclusions
In this study, the effects of Na2O concentration and w/b ratio on
the phase evolution and carbonation in alkali-activated slag/fly ash
cements are studied. In AAS, the Na2O concentration of activators
(4–8%) has little influence on the type of reaction products. When
the Na2O concentration increases from 4% to 8%, the amount of C-
A-S-H gels increases due to a higher reaction degree; this effect is
more evident when the Na2O concentration increases from 4% to
6%. Therefore, the amount of calcium carbonates after carbonation
increases with the increased Na2O concentration, especially when
the Na2O concentration increases from 4% to 6%. However, the
Na2O concentration has little influence on the formation rate of
calcium carbonates in AAS pastes, and the crystallinity of calcium
carbonates formed during carbonation is the highest when the
Na2O concentration is 4%. When the content of slag is 60%, the
increased Na2O concentration from 6% to 8% is beneficial to the
reaction of fly ash and the formation of more N-A-S-H gels; thus,
the formation rate of calcium carbonates decreases but the amount
and crystallinity of calcium carbonates change little. When the
content of slag is 20%, the formation rate of calcium carbonates
decreases significantly with the increased Na2O concentration
from 6% to 8%.
J. Zhang, C. Shi and Z. Zhang Construction and Building Materials 269 (2021) 121258

Fig. 12. FTIR spectra of carbonated alkali-activated cements, (a) S100W0.3, (b) S100W0.5, (c) S60W0.3, (d) S60W0.5, (e) S20W0.3, (f) S20W0.5.

When the w/b ratio decreases from 0.5 to 0.3, the amount of w/b ratio, the formation rate of calcium carbonates decreases,
crystalline phase products in AAS decreases, but the C-A-S-H but the crystallinity of calcium carbonates becomes lower. With
phases have a higher extent of formation. With the decreased the incorporation of fly ash, the reaction degree of slag and fly

13
J. Zhang, C. Shi and Z. Zhang Construction and Building Materials 269 (2021) 121258

Fig. 13. DTG of carbonated alkali-activated cements, (a) S100W0.3, (b) S100W0.5, (c) S60W0.3, (d) S60W0.5, (e) S20W0.3, (f) S20W0.5.

ash is higher when the w/b ratio is 0.3. When the content of slag is ratio from 0.5 to 0.3; when the content of slag is 20%, the amount
60%, the formation rate of calcium carbonates decreases but the of calcium carbonates increases, but the formation rate of calcium
amount of calcium carbonates increases with the decreased w/b carbonates changes little.
14
J. Zhang, C. Shi and Z. Zhang
Fig. 14. Content of calcium carbonates and fitting curves in carbonated alkali-
activated cements with different w/b ratios.
CRediT Author statement
Jian Zhang: Writing - original draft. Caijun Shi: Writing -
review & editing. Zuhua Zhang: Writing - review & editing.
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 thank financial support by the National Science
Foundation of China under projects of Nos. 51638008 and
51878263, and the Joint Open Fund of Jiangsu Collaborative Inno-
vation (JH201802). The participation of Z. Z. is partially funded by
the Australian Research Council DECRA (DE170101070) and Dis-
covery project (DP160104149).
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