Waste and Biomass Valorization (2020) 11:3007–3020

https://doi.org/10.1007/s12649-019-00579-z

ORIGINAL PAPER

Effects of Alkali Activation and ­CO2 Curing on the Hydraulic Reactivity

and Carbon Storage Capacity of BOF Slag in View of Its Use in Concrete
M. Morone1 · Ö. Cizer2 · G. Costa1   · R. Baciocchi1

Received: 3 August 2018 / Accepted: 2 January 2019 / Published online: 25 January 2019
© Springer Nature B.V. 2019

Abstract
This work investigates the sequential application of alkali activation and C ­ O2 curing to BOF steel slag as a technique for
improving its hydraulic reactivity for use in concrete, while also exploiting its potential as a carbon sink. Activation with
either a sodium hydroxide/sodium-silicate or a sodium hydroxide/sodium carbonate solution was first evaluated in a prelimi-
nary calorimetric study for selecting the solution compositions leading to the formation of early stage hydration products.
The pastes produced with the selected solutions were then cured either in a humidity chamber or in a carbonation chamber
(at 20 or 50 °C) for up to 28 days, in order to assess long term reaction products. Mineralogical and thermal analysis showed
the formation of a C–S–H like phase, specifically in the samples activated by the sodium hydroxide/sodium-silicate solu-
tion, whereas significant occurrence of gaylussite was noticed in the samples activated with the sodium hydroxide/sodium
carbonate solution. A maximum ­CO2 uptake of 6% by wt, due to calcium carbonate formation, was observed in the latter
samples, whereas a 5% value was achieved in the former ones. The compressive strength of the mortars prepared with
sodium hydroxide/sodium silicate and cured in the carbonation chamber at 50 °C was above 2 MPa, while it was lower for
the other samples, particularly those activated with sodium hydroxide/sodium carbonate. Alkali activation employing sodium
hydroxide/sodium silicate solutions followed by C ­ O2 curing at relatively high temperature (i.e. 50 °C) resulted a promising
treatment for BOF slag valorization in the manufacturing of concrete for non structural applications.

Keywords  BOF steel slag · Alkali activation · Curing · CO2 uptake · Compressive strength · Hydraulic reactivity

Statement of Novelty Introduction

Fundamental study on the reactivity of a crystalline residue Significant amounts of alkaline solid residues are generated
(BOF slag) towards alkali activation for enhancing hydraulic by the steelmaking industry, with values ranging between
reactivity. ­CO2 curing also tested to improve strength and 10 and 15% by weight of the produced steel, depending on
store ­CO2. the characteristics of the manufacturing process [1]. One of
the most abundant and scarcely reused by-products is basic
oxygen furnace (BOF) slag, generated during the conversion
of iron ores into steel in basic oxygen converters. Referring
to EU data of 2016, BOF slag represents more than 50%
of the total steel slag production (18.4 million tons) [2], of
which roughly 25% is typically landfilled after undergo-
* R. Baciocchi
baciocchi@ing.uniroma2.it ing a metal recovery step [3], or at best reused for low end
applications. In order to improve the current management
G. Costa
costa@ing.uniroma2.it practices for BOF slag, different experimental studies have
focused on the possibility of using these materials in civil
1
Laboratory of Environmental Engineering, Department engineering applications. In particular, the options tested
of Civil Engineering and Computer Science Engineering, include its use as Ca(OH)2 source for activating blast furnace
University of Rome “Tor Vergata”, Rome, Italy
slag (BFS) in order to obtain a hydraulic road binder [4], as
2
Department of Civil Engineering, KU Leuven, partial replacement of coarse aggregates in asphalt mixtures
3001 Heverlee, Belgium

13
Vol.:(0123456789)

3008
[5, 6] or as partial replacement of cement in concrete, upon
rapid quenching outside the furnace [7]. Nevertheless, some
properties of this type of residue, namely its high volumetric
expansion and poor hydraulic activity, still hinder its use in
civil engineering applications.
The main constituent (in terms of oxide content) of BOF
slag is CaO, with contents ranging from 37 to 52%, followed
by ­Fe2O3 (7–38%), ­SiO2 (8–18%) and MgO (0.8–14.1%) [8].
Ca and Mg components are mostly in the form of silicates;
however for this type of slag, significant contents of free
calcium and magnesium oxides have been reported. This is
an important aspect to take into account for the use of BOF
slag in bound (e.g. aggregates used in concrete production
with binding agents, such as cement) or unbound applica-
tions (e.g. aggregates used as received, as filling material in
road base layers) [9]. Short-term hydration and long-term
carbonation reactions of free lime can result in the swelling
of the slag over time, leading to a poor volumetric stabil-
ity and hence to low technical performance of the material.
On the other hand, although the presence of dicalcium-sili-
cate may suggest cementitious properties [10], BOF slag is
characterized by slow hydration kinetics and hence a poor
hydraulic activity, owing to a high content of iron oxide, that
is not reactive with water, and low content of tri-calcium sili-
cate, known for rapid hydration and strength development in
cement [11, 12]. In this regard, different experimental stud-
ies performed on BFS, which is typically used in concrete
manufacturing as a partial replacement of Portland cement,
showed that alkali activation can be an effective treatment
to stimulate the material’s latent pozzolanic properties and
to improve its mechanical performance [13]. Alkali activa-
tion is a chemical process in which the raw material, usually
amorphous (e.g. BFS or fly ash), is mixed with specific alka-
line solutions (e.g. sodium or potassium hydroxides, carbon-
ates or silicates) in order to favor the dissolution of reacting
species and to enhance hydration reactions [14]; these reac-
tions lead to the formation of binding phases that yield a
compact and strong product, such as calcium aluminosilicate
hydrate (C–A–S–H) gel, in the case of systems with high Ca
contents such as BFS, or alkali aluminosilicate (N–A–S–H)
gel, for systems that present low Ca contents such as fly ash
[15]. This treatment has been widely investigated in order
to identify alternative binders instead of cement for concrete
production, with the aim of achieving a reduction of the car-
bon footprint and an increase in the durability of the product
[16]. The calcium(-sodium) aluminosilicate hydrated type
gel formed in these systems presents a relatively lower Ca
content compared to the C–S–H gels formed in Portland
cement, and is characterized by the presence of alumino-
silicate chains (which may be cross-linked or not) [17]. The
final product’s mechanical properties were found to depend
on the starting material’s composition, activator type and
concentration, curing conditions and pH [18, 19]. According
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Waste and Biomass Valorization (2020) 11:3007–3020
to Fernández-Jiménez et al. [20], the most important fac-
tors that affect the mechanical strength of alkali activated
BFS mortars are the type and concentration of the alkaline
activator. It was observed that slag activation with a mixture
of ­Na2SiO3·H2O and NaOH allowed to obtain the reaction
product presenting the highest mechanical strength, also in
terms of early-age (3 days) strength development [20]. The
use of sodium carbonate was found to lead to an increase of
mechanical strength only for longer curing times, due to the
formation of carbonates [20, 21]. Most of the works regard-
ing the effects of alkali activation considered amorphous res-
idues, such as BFS; only few studies investigated crystalline
residues rich in Ca and Si, such as by-products of the steel
making process (i.e. continuous casting slag or AOD slag),
with the aim of producing a valuable final product. Namely,
Salman et al. [22, 23] pointed out that the treatment of crys-
talline and non-hydraulic stainless steel slag with alkalis and
steam curing favored the development of hydration reactions
and allowed to achieve a dense and strong solid, consisting
of a calcium silicate hydrate matrix. Significant cementi-
tious properties of ladle slag activated with a sodium silicate
solution and cured at room temperature were also reported
by Shi [10], suggesting the possibility to apply this process
also to non amorphous residues, such as crystalline BOF
steel slag.
As for all cementitious materials, it is common practice
to combine the alkali activation treatment with a curing
process, in order to allow the completion of hydration
reactions. Curing has a strong influence on the properties
of the treated sample. The optimization of the operating
conditions, such as relative humidity, temperature, time
of exposure and C ­ O 2 concentration, is needed to attain
a final product with adequate technical properties [24].
Most of the experimental studies on alkali activated slag
were performed by placing the samples in a curing cham-
ber at ambient temperature (usually T = 20 °C) and high
relative humidity, i.e. 90% [25]. Regarding the effects of
the curing temperature, Fernández-Jiménez et al. reported
that increasing the temperature (from 25 to 45 °C) had
a positive effect on the early strength of activated BFS,
regardless the type of activator employed, although at
later curing times, the effect seemed to reverse [20]. Shi
et al. [26] and Zhan et al. [27] showed that carrying out
the curing treatment under a C ­ O2 rich atmosphere allowed
to obtain concrete blocks with a higher earlier compres-
sive strength with respect to the ones obtained by steam
curing. The authors also found that the ­CO 2 sequestra-
tion of concrete blocks increased for longer C ­ O2 curing
times, suggesting that this method could also be suitable
for storing C­ O2. In this regard, owing to the fact that BOF
slag has a typically alkaline nature and an abundance of
phases containing calcium and magnesium that are poten-
tially reactive towards C ­ O2, it should be possible to take
Waste and Biomass Valorization (2020) 11:3007–3020 3009
advantage of the required curing step as a valuable tech-
nique for storing C­ O2 in a thermodynamically stable and
solid form. Baciocchi et al. [28] carried out accelerated
carbonation tests in a static reactor under wet conditions,
i.e. applying a liquid to solid (L/S) ratio lower than 1 l/
kg, on two types of BOF steel slag and found that, at mild
operating conditions (T = 50 °C; p = 10 bar), the residue
exhibited a significant ­CO2 sequestration capacity, reach-
ing an uptake of 20–21% after 24 h of carbonation. In this
context, alkali activation may also contribute in promot-
ing the uptake of ­CO2 by increasing the alkalinity of the
aqueous solution in contact with the slag material.
This work investigates the sequential combination of
alkali activation and ­CO2 curing applied to BOF steel slag
as a technique for improving the hydraulic reactivity of
these residues in view of their use in concrete, while also
exploiting their potential as a carbon sink. To this aim,
different tests were performed on BOF slag changing the
type and concentration of the alkali activator solution and
the operating conditions of the curing step, i.e. tempera-
ture, duration and C ­ O2 concentration. First, a calorimet-
ric study was performed with the aim of analyzing the
evolution of early hydration reactions and to select the
alkaline solutions providing a faster hydration rate. Then,
based on the results of this first screening phase, paste
specimens obtained by mixing the slag with the selected
alkaline solutions were tested in order to investigate the
long term effect of the combined treatment on product
properties. Namely, the products obtained were character-
ized by X-ray diffraction (XRD) and thermal gravimetric
analysis (TGA) in order to detect the main crystalline
and amorphous phases formed. Besides, the ­CO2 uptake
was measured with the aim of assessing the potential of
the tested pastes as carbon sink. Finally, mortar speci-
mens were prepared again by mixing the slags with the
selected alkaline solutions and their compressive strength
was assessed in order to gain insight on the potential of
the proposed process to yield a product with mechanical
properties suitable for civil engineering applications.
Table 1  Activator type and Activator type and molarity
corresponding molarity,
weight ratio, silica modulus NaOH (2 M) + Na2SiO3
and identification code of the
NaOH (2 M) + Na2SiO3
alkaline solutions adopted in the
screening phase NaOH (4 M) + Na2SiO3
NaOH (4 M) + Na2SiO3
NaOH (2 M) + Na2CO3 (1 M)
NaOH (2 M) + Na2CO3 (1 M)
NaOH (4 M) + Na2CO3 (2 M)
NaOH (4 M) + Na2CO3 (2 M)
Materials and Methods
Materials and Alkali Solutions
The BOF slag sample employed in this study was collected
at the outlet of the BOF unit of an Italian steel plant employ-
ing the integrated steelmaking process, after crushing and
magnetic separation for iron and metal recovery.
The composition of the alkaline solutions tested in the
screening phase, aimed at investigating early hydration reac-
tions, is summarized in Table 1. A first activator was pre-
pared by mixing a NaOH solution (2 M or 4 M), prepared
by dissolving NaOH pellets (Fisher Scientific, 99.4% purity)
in deionized water, with a commercial solution of ­Na2SiO3
(ABCR Gmbh Co. KG, water glass, 39–40% silicates in
water), at a 50:50 or 75:25 weight ratio. The silica modu-
lus of each solution, expressed as the molar ratio of ­SiO2
and ­Na2O, is reported in Table 1. A second activator type
was obtained again starting from a 2 M or 4 M NaOH solu-
tion, which was mixed with a 1 M or 2 M N ­ a2CO3 solution,
respectively, again at a 50:50 or 75:25 weight ratio. Besides,
for both types of alkaline activators, the concentration of the
sodium hydroxide solution was kept below 5 M, as above
this threshold efflorescence phenomena were reported [29].
Experimental Methods
Characterization of the Untreated Slag
The particle size of the BOF slag samples was determined
by applying the ASTM D422 standard procedure. The
elemental composition of the material was determined by
alkaline digestion with ­Li2B4O7, in platinum melting pots at
1050 °C, followed by dissolution of the molten material in
a 10% H­ NO3 solution and measurement of element concen-
trations by ICP-OES using a Agilent 710-ES spectrometer.
The mineralogical composition of all samples was evalu-
ated by powder XRD analysis with Cu Kα radiation using
a Philips Analytical PW 1710 diffractometer, operating at
45 kV and 35 mA, with an angular step of 0.02° held for 2 s
Weight ratio Silica modulus Code
50:50 2.3 NH (2 M) + NS_50:50
75:25 1.4 NH (2 M) + NS_75:25
50:50 1.7 NH (4 M) + NS_50:50
75:25 0.85 NH (4 M) + NS_75:25
50:50 – NH (2 M) + NC (1 M)_50:50
75:25 – NH (2 M) + NC (1 M)_75:25
50:50 – NH (4 M) + NC (2 M)_50:50
75:25 – NH (4 M) + NC (2 M)_75:25
13

3010
over a range of 5°–75° 2θ. The inorganic carbon (IC) content
was evaluated by using a Shimadzu TOC VCPH analyser
equipped with a SSM-5000A solid sampler.
Screening Phase: Paste Preparation and Calorimetric Test
Early hydration kinetics were investigated through isother-
mal conduction calorimetry, carried out in a TAM Air device
(TA instrument), by preparing pastes made up of a mixture
of slag and alkaline activators. For the preparation of paste
samples the slag fraction with a particle size < 0.25 mm, cor-
responding to 41% by wt of the overall BOF sample, was
used. The pastes were prepared by mixing 10 g of solid with
the alkali solutions reported in Table 1, keeping the liquid to
slag ratio equal to 0.3 l/kg, set on the basis of the workability
of the mixture. The calorimetric tests were carried out at 20
and 50 °C, in order to assess the effect of temperature on the
rate of hydration of BOF slags.
Identification of Long‑Term Reaction Products: Paste
Preparation and Testing
The evaluation of the long-term reaction products was car-
ried out by preparing paste specimens (2.5 × 2.5 × 2 cm3)
consisting of a mixture of about 15 g of BOF slag with the
alkaline solutions that showed the highest degree of hydra-
tion in the calorimetric study. For these tests the solution/
slag ratio was decreased (from 0.3 to 0.2 l/kg) in order to
ensure the workability of the mixtures. It should be noted
that this modification may affect hydration kinetics, how-
ever since the liquid to slag ratio was modified in the same
way for all of the second type of tests, the relative results in
terms of effects of the alkaline solutions and curing condi-
tions employed, should not be influenced. Control samples
prepared by mixing the slag with water employing a liquid
to solid ratio of 0.2 l/kg were also carried out and used as
reference. The pastes were cured at the following operating
conditions:
– in a humidity chamber (HC), at a relative humidity of
98% and a temperature of 22 °C;
– in a carbonation chamber at a temperature of 20  °C
(CC20), ­CO2 concentration of 5% and relative humidity
of 75% (kept constant by using a saturated ­K2CO3 solu-
tion);
– in a carbonation chamber at 50 °C (CC50), by keep-
ing the remaining operating conditions equal to those
adopted in CC20.
The samples were removed from the chambers after 3, 7
and 28 days of curing and then ground in an agate mortar
and vacuum dried (Alpha 1–2 LD, Martin Christ instrument)
for 2 h at the total pressure conditions (0.011 mbar) that
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Waste and Biomass Valorization (2020) 11:3007–3020
allowed to remove the free water content and stop further
hydration reactions [30]. Then, the crushed pastes were ana-
lysed using TGA and XRD in order to identify the reaction
products obtained at the different tested conditions.
TGA was carried out with a Netzsch STA 409 PC DSC-
TGA equipment in a pure ­N2 atmosphere at 60 ml/min,
over a temperature range of 20–1000 °C and at a heat-
ing rate of 10 °C/min. The differential thermal gravimetry
(DTG) data were used to identify the reaction products.
The mineralogical analysis of the treated samples was
evaluated by using the same method adopted for the slag
samples (see “Characterization of the Untreated Slag” sec-
tion). The degree of carbonation of the BOF slag pastes
was calculated by applying the following equation:
CO2 final (%) − CO2 initial (%)
CO2 uptake (%) = × 100 (1)
100 − CO2 final (%)
where ­CO2 initial and C
­ O2 final represent respectively the car-
bon dioxide content of the untreated and treated samples
evaluated from the IC content, measured with a Shimadzu
TOC VCPH analyser equipped with a SSM-5000A solid
sampler.
Mortars Preparation and Testing
The compressive strength was evaluated with the EN 196-1
standard method on mortar samples prepared as follows.
First, the slag sample was mixed with 0–2 mm river sand
at a ratio equal to 0.3 ­kgslag/kgsand; then, the alkaline solu-
tion was added to the solid mixture at a liquid-to-solid ratio
equal to 0.2 l/kg, that proved to be the optimum value for
a good workability of the mortars. Each alkali activated
mixture was cast in three steel molds (4 × 4 × 16 cm3) and
compacted for 3 min in a jolting machine so to remove air
bubbles. Based on the results obtained for the slag pastes, it
was expected that the mortar specimen would not acquire a
suitable mechanical resistance if cured in the HC; hence the
mortars were cured only in the carbonation chambers (either
at 20 or at 50 °C), adopting the same conditions used for the
slag pastes. Furthermore, after a first hardening phase, the
mortar beams were cut in four cubes (4 × 4 × 4 cm3), and
then placed back into the C­ O2 chambers to complete curing.
The mechanical strength of the mortar cubes was
assessed in duplicate by using the Schenck-RM 100 com-
pression testing machine, with a loading rate of 2 mm/
min. The pore size distribution of the mortar samples was
evaluated in duplicate by Mercury Intrusion Porosimetry
(Micrometrics AutoPore IV 9500) on samples dried at
40 °C to constant weight. The instrument was composed
of a low (until 3 bar) and a high (until 200 bar) pressure
unit, while the contact angle of the Hg was set to 130°.
Waste and Biomass Valorization (2020) 11:3007–3020 3011

Results and Discussion slag sample was characterized by a crystalline nature, with

the main phases detected being dicalcium silicate (larnite),
Characterization of Untreated Slag wüstite (FeO), Ca–Al–Fe oxide ­(Ca2Fe1.4Al0.6O5), srebro-
dolskite ­(CaFeO4) and traces of portlandite.
The untreated BOF slag sample showed a particle size
smaller than 2 mm with a mean diameter equal to 0.35 mm. Screening Phase: Calorimetric Study
The main chemical constituents of the BOF slag, reported
in Table 2, were Ca (265 g/kg) and Fe (221 g/kg), followed Figure 2 reports the heat release patterns corresponding to
by Mg (45.7 g/kg) and Mn (41.5 g/kg), similar to the values early hydration of the BOF slag pastes, activated with both
reported in Baciocchi et al. [28]. The XRD pattern of the types of alkaline mixtures. Looking specifically at Fig. 2a,
BOF slags is reported in Fig. 1. It is evident that the BOF c, an initial very early sharp peak was observed for all the
mixtures considered, that can be associated to the initial dis-
solution of the material [31]. This initial peak was followed
by a period characterized by a slow reaction rate (induction
Table 2  Elemental composition of the as-received BOF slag sample, period) whose duration was reported to depend on the type
expressed as g/kg for major elements and as mg/kg for trace elements of alkali activator used [31].
BOF slag The samples activated with the sodium hydroxide/sodium
silicate solutions exhibited different exothermic peaks, asso-
Major elements (g/kg)
ciated to the precipitation of the reaction products (Fig. 2a).
 Al 9.7
The longest delay period and the highest peak were observed
 Ca 265
for the activating solution containing NaOH 4 M at 75%
 Fe 221.2
by wt, while a very broad and low peak was detected when
 K 0.58
the BOF slag was activated with a solution presenting the
 Mg 45.7
same NaOH molarity but a higher amount (50% by wt) of
 Mn 41.45
the silicate solution. Conversely, two early (before 200 h)
 Na 1.86
consecutive peaks were observed when the BOF slag was
 Si 22
activated with the solutions containing NaOH 2 M; these
Trace elements (mg/kg)
were more evident for the 75% NaOH solution, while a third
 Ba 56.5
exothermic peak with a longer delay period was observed
 Cd 193.1
for the binder with a 50% NaOH content. Shi and Day [32]
 Cr 1343.1
observed the presence of large peaks when BFSs were acti-
 Cu 273.5
vated with a sodium silicate solution at different molarities,
 V 530.2
and associated this behaviour to the wetting and dissolution
 Zn 281.1
of slag grains and formation of primary C–S–H as Ca is

Fig. 1  XRD pattern of the as- d,p

received BOF slag
d
h,f
h,i a,d m
b,e,p

h b,m,p d
b,d a,h,i m
b,e d b,d e
a n d e
d,p b,n

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
2θ (°)
Legend: a)portlandite (Ca(OH)2); b)diopside, aluminan (Ca(Mg,Al)(Si,Al)2O6; d)beta-larnite
(Ca2SiO4); e)magnete (Fe3O4); f)bredigite (Ca14Mg2(SiO4)8); h)Calcium aluminum iron oxide
(Ca2Fe1.4Al0.6O5); i)srebrodolskite (CaFeO4); m) wüste (FeO); n)hemate (Fe2O3);
p) fayalite ((Fe,Mg)2SiO4)

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3012 Waste and Biomass Valorization (2020) 11:3007–3020

0.6 45
(a) (b)
36

Cumulave heat flow (J/g)

0.4
27
Heat flow (J/h*g)

18
0.2

0 0
0 48 96 144 192 240 288 336 0 48 96 144 192 240 288 336
Time (hours) Time (hours)

NH (2M) + NS_50:50 NH (2M) + NS_75:25 NH (4M) + NS_50:50 NH (4M) + NS_75:25

0.6 45
(c) (d)
36

Cumulave heat flow (J/g)

0.4
27
Heat flow (J/h*g)

18
0.2

0 0
0 48 96 144 192 240 0 48 96 144 192 240
Time (hours) Time (hours)

NH (2M) + NC (1M)_50:50 NH (2M) + NC (1M)_75:25 NH (4M) + NC (2M)_50:50 NH (4M) + NC (2M)_75:25

Fig. 2  Heat flow and cumulative heat flow curves at 20 °C of BOF slag pastes activated with different molar and weight ratios of: a, b a mixture
of NaOH (NH) and ­Na2SiO3 (NS); c, d a mixture of NaOH (NH) and N ­ a2CO3 (NC)

incorporated into the gel, but also to ­SiO44− polymerization the system activator (­ Na2CO3 solution) and a retarded and
in the solution for high water glass concentrations. How- lower in height peak compared to that determined employing
ever in this study, for all the tested solutions, the cumula- a NaOH + Na2SiO3 solution, possibly denoting a delay in
tive heat release pattern (Fig. 2b) showed that after 240 h dissolution/hydration due to the lower pH of the carbonate-
of hydration a plateau was not achieved, suggesting a rela- based activating solution. Also in this work the cumulative
tively slow hydration kinetics of the activated samples. The heat flow curves (reported in Fig. 2d) showed a lower overall
highest cumulative heat release was observed for the NH intensity than the one observed for the pastes mixed with
(2 M) + NS_50:50 solution, which was also characterized the sodium hydroxide/sodium silicate solution (see Fig. 2b).
by the highest silica modulus. Krizan and Zivanovic [25] Although exothermic peaks were detected upon the acti-
found a positive correlation between the silica modulus of vation of BOF at 20 °C, the cumulative heat release, mainly
the solution and the heat released from activated BFS and for the samples activated with the sodium hydroxide/sodium
attributed this finding to the faster hydration rate of the cal- carbonate solutions, showed rather low values. This effect
cium silicate compounds. may be attributed to a slow reaction rate at ambient tem-
The results achieved for the BOF pastes activated with perature, which does not allow for sufficient dissolution of
the sodium hydroxide/sodium carbonate solutions at differ- silicates and, subsequently, precipitation of the main reactive
ent molar and weight ratios are reported in Fig. 2c, d. In this and hardening phases of the slag, as also reported in other
case, after the initial intense peak associated once again with studies [32].
the initial dissolution of the material, no appreciable peaks Figure 3 reports the heat release pattern for the same
were observed with a constant heat flow detected during alkali activated slag pastes at 50 °C. As far as the sodium
the whole testing time. Garcia-Lodeiro et al. [33], working hydroxide/sodium silicate solutions are concerned (see
on a mixture of cement and fly ash activated with a sodium Fig. 3a), it can be observed that the heat flow patterns were
carbonate solution, found two early peaks associated with characterized by two main peaks. The highest one was

13
Waste and Biomass Valorization (2020) 11:3007–3020 3013

5
5000 100
100000
(a) (b)

Cumulave heat flow (J/g)

4
4000 80
80000

3
3000 60
60000
Heat flow (J/h*g)

2
2000 40
40000

1
1000 20
20000

0 0
0 48 96 144 192 0 48 96 144 192
Time (hours) Time (hours)

NH (2M) + NS_50:50 NH (2M) + NS_75:25 NH (4M) + NS_50:50 NH (4M) + NS_75:25

50005 100000
100
(c) (d)

Cumulave heat flow (J/g)

40004 80000
80

30003 60000
60
Heat flow (J/h*g)

20002 40000
40

10001 20000
20

0 0
0 48 96 144 192 0 48 96 144 192
Time (hours) Time (hours)

NH (2M) + NC (1M)_50:50 NH (2M) + NC (1M)_75:25 NH (4M) + NC (2M)_50:50 NH (4M) + NC (2M)_75:25

Fig. 3  Heat flow and cumulative heat flow curves at 50 °C of BOF slag pastes activated with different molar and weight ratios of: a, b a mixture
of NaOH (NH) and ­Na2SiO3 (NS), c, d a mixture of NaOH (NH) and N ­ a2CO3 (NC)

observed for a sodium hydroxide concentration of 2 M at
50% by wt after 72 h of reaction. In general, the intensity of
the peaks and the cumulative heat were notably higher than
the ones observed at 20 °C. This confirmed that a tempera-
ture increase implies the acceleration of the dissolution and
hydration reactions and, hence, the quick formation of reac-
tion products, as confirmed in studies carried out on different
types of solid mixtures [32, 34].
The highest cumulative heat, obtained after 192 h of reac-
tion, resulted for the solution containing 2 or 4 M NaOH
with a 50:50 ratio with silicates. This finding suggests that
at 50 °C a higher silicate content affected the slag’s reactiv-
ity probably owing to a higher dissolution of silica leading
to increased C–(N)–A–S–H formation. Also in a previous
study the use of sodium silicate was found to increase the
reactivity of BFS especially at elevated temperature [35].
It should be noted that this result differed from those of the
tests performed at 20 °C for which both 2 M NaOH solu-
tions yielded a slightly higher heat release compared to the
4 M ones.
Concerning the pastes activated with the sodium hydrox-
ide/sodium carbonate mixtures, the general shape of both
heat flow and cumulative heat flow curves at 50 °C (see
Fig. 3c, d) was considerably similar to that determined at
low temperature, although in the former case a five times
higher heat intensity was retrieved, indicating a somehow
faster dissolution of reactive phases. For this type of system
the higher molarity of the NaOH solution may have started
to promote the dissolution of reacting phases by increas-
ing the solution’s pH, which as discussed above is lower in
carbonate-containing binding solutions.
Identification of Long‑Term Reaction Products
Based on the results achieved in the screening phase, two
alkali activator mixtures (NaOH (2 M) and N ­ a2SiO3, 50:50,
labelled as SS and NaOH (4 M) and ­Na2CO3 (2 M), 75:25,
labelled as SC) were selected to prepare pastes with the
aim of identifying long-term reaction products generated
under different curing conditions, i.e. in the HC, or in the

13

3014
carbonation chamber at 20 °C (CC20), or at 50 °C (CC50)
and times (3, 7 and 28 days).
Thermal Analysis Results
Figure 4 reports the DTG results obtained on the BOF slag
pastes mixed with water or activated with the two selected
alkaline solutions and cured either in the HC or in the car-
bonation chamber.
It can be observed that different phases were formed
upon alkali activation and C ­ O2 curing, the nature of which
depends on the type of activator solution and curing condi-
tions applied. Three main peaks were observed for all cur-
ing times and conditions when the pastes were mixed with
water only (first row of Fig. 4). An initial one, characterized
by a very low intensity, was observed at around 100 °C.
This peak can be attributed in general to either adsorbed
(or free) water or calcium silicate hydrate-like phase. Since
the samples were freeze-dried in this case the peak may be
associated to the latter phase. The formation of a C–S–H
like phase was identified also in other studies [36, 37], as the
product of BOF slag hydration reactions, where however it
was observed as an impure form containing also other ele-
ments, such as Fe, Al and Mg. A second peak was observed
at around 400 °C at early curing times for the samples cured
in the HC and in the carbonation chamber at 20 °C; this
peak, whose position corresponds to the decomposition tem-
perature of portlandite, disappeared after 28 days of curing,
whereas a third peak at 650 °C, clearly related to the for-
mation of calcium/magnesium carbonates, was observed to
increase for longer curing times. However, for the samples
cured in the carbonation chamber at 50 °C, this peak showed
a similar intensity for all the curing times and was higher
than for the other curing conditions, proving that the main
effect of increasing the curing temperature in a C ­ O2 rich
environment was the quick formation of calcium carbonate,
already very clearly observed after 3 days of curing.
The main effect related to activation with the sodium
hydroxide/sodium silicate solution (second row of Fig. 4)
was the appearance, both in the HC and carbonation cham-
ber at 20 °C, of a peak at around 100 °C, which corresponds
to the dehydration of bound water in C–S–H type reaction
products [38]. This phase is a hydration product which was
reported to form as a result of the hydration and activation
of the crystalline calcium silicate phases present in the slag,
as reported by Salman et al. [22, 23], but also of the dissolu-
tion of Ca from portlandite and other oxide phases present
in the slag which react with silica in the solution. Formation
of calcite, identified by the peak at around 650–700 °C, was
instead observed at all curing conditions, regardless of the
temperature adopted.
The thermal analysis results obtained by mixing the BOF
slag paste with the sodium hydroxide/sodium carbonate
13
Waste and Biomass Valorization (2020) 11:3007–3020
solution (third row of Fig. 4) showed that most of the mass
loss from the samples cured in the humidity and in the car-
bonation chamber at 20 °C occurred at temperatures below
200 °C. For these curing conditions, a narrow peak was
observed at around 100–120 °C, whose intensity showed
to be highly similar for all curing times. This peak, whose
shape resulted sharper than the one observed for the sam-
ples activated with the Na-silicate solution, was in this case
associated to gaylussite (­ Na2Ca(CO3)2·5H2O) [39]. There is
in fact evidence in other literature studies of the occurrence
of this phase as a product of the hydration [33] and carbona-
tion [40] reactions of BFS activated with a sodium carbon-
ate solution. Its formation may be ascribed to an additional
supply of carbonate ions resulting from the dissociation of
­Na2CO3, along with those obtained from the dissolution
of ­CO2 that, in combination with the C ­ a2+ obtained from
the solid dissolution, forms such a carbonate phase [33].
In addition, it was observed that the intensity of this peak
was lower at higher curing temperature. In this case, for all
the curing times tested, a small shoulder at around 180 °C
was also noticed, which can be once again associated to the
loss of water from a hydrated sodium–calcium carbonate
phase [39]. Finally, for all the tested curing conditions, a
second main peak at around 650 °C was observed, which
is related to the decomposition temperature of calcium car-
bonate. At ambient ­CO2 curing temperature, the amount of
calcium carbonates showed to increase with time for a cur-
ing period up to 7 days, remaining constant until 28 days,
indicating an increased carbonation of the slag paste with
time. Conversely, similar intensities for all the curing times
tested were obtained at higher curing temperature, probably
related to an enhanced early-age carbonation kinetics com-
pared with the samples cured in the ­CO2 chamber at ambient
temperature.
Mineralogical Analysis Results
Figure 5 reports the mineralogy of the BOF pastes activated
with both alkali solutions, cured for 7 and 28 days at all
the tested curing conditions compared with the one of the
untreated BOF slag. Upon alkali activation with the sodium
hydroxide/sodium silicate solution (see Fig. 5a), the occur-
rence of calcite peaks was observed for all curing condi-
tions. The XRD plots were also characterized by a broad
hump (44°–52° 2θ), which may be attributed to formation of
an amorphous phase, likely a C–(N)–A–S–H type reaction
product. Calcite was also observed in the samples activated
with the sodium hydroxide/sodium carbonate solution (see
Fig. 5b), with a higher intensity of the peaks for a higher
curing temperature. Peaks corresponding to gaylussite were
also detected in agreement with the results provided from
the DTG analysis. It is worth noting that these peaks were
observed only for the samples cured either in the HC or in
Waste and Biomass Valorization (2020) 11:3007–3020 3015

Fig. 4  DTG of BOF slag pastes Water

mixed with water (first row)
or activated with the NaOH
2 M + Na2SiO3_50:50 (SS) (a) (b) (c)
solution (second row) and
with the NaOH 4 M + Na2CO3 3 days 3 days 3 days
4 M_75:25 (SC) solution (third
row) and cured in: a the humid-
ity chamber and in the carbona-

DTG (% by wt./°C)

DTG (% by wt./°C)
tion chambers at a temperature 7 days 7 days 7 days

DTG (% by wt./°C)
of b 20 °C and c 50°C

28 days 28 days 28 days

0.05 0.05 0.05

0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature (°C) Temperature (°C) Temperature (°C)

NaOH 2M + Na2SiO3_50:50

(a) (b) (c)

3 days 3 days 3 days
DTG (% by wt./°C)

DTG (% by wt./°C)
7 days
DTG (% by wt./°C)

7 days 7 days

28 days 28 days 28 days

0.05 0.05 0.05

0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature (°C) Temperature (°C) Temperature (°C)

NaOH 4M + Na2CO3 4M_75:25

(a) (b) (c)

3 days 3 days 3 days

7 days 7 days 7 days

DTG (% by wt./°C)

DTG (% by wt./°C)
DTG (% by wt./°C)

28 days 28 days 28 days

0.05 0.05 0.05

0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature (°C) Temperature (°C) Temperature (°C)

13

3016 Waste and Biomass Valorization (2020) 11:3007–3020

Fig. 5  XRD pattern of the (a)

untreated BOF slag and the d,p
c d h,f b,e,p d
BOF slag pastes activated with h a,d
a the SS solution and b SC n q b,d b,m,p m m
solution and cured, at different h a d c,d,p d h,i c e e 28d_CC50
times, in the humidity chamber
(HC), carbonation chamber 7d_CC50
at 20 °C (CC20) and 50 °C
(CC50) 28d_CC20

7d_CC20

28d_HC

7d_HC

Untreated slag

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
2θ (°)

g,u
(b) c

d,p
h,f,u
b,e,p c,d,pm
h b,e d d b,m,p
c n q d c dh c e me 28d_CC50

7d_CC50
u u 28d_CC20

7d_CC20

28d_HC

7d_HC

Untreated slag

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
2θ (°)

Legend: a)portlandite (Ca(OH)2); b)diopside, aluminan (Ca(Mg,Al)(Si,Al)2O6; c)calcite (CaCO3); d)beta-larnite

(Ca2SiO4); e)magnete (Fe3O4); f)bredigite (Ca14Mg2(SiO4)8); g) anorthite sodian ((Ca,Na)(Si, Al)4O8; h)calcium
aluminum iron oxide (Ca2Fe1.4Al0.6O5); i)srebrodolskite (CaFeO4); m) wüste (FeO); n)hemate (Fe2O3); p)
fayalite ((Fe,Mg)2SiO4); q) ferrobustamite ((Ca,Fe,Mn)3Si3O9); u) gaylussite (Na2Ca(CO3)2•5H2O)

the carbonation chamber at 20 °C. Moreover, for the lat-
ter curing condition, the ratio between the intensities of the
peaks of gaylussite and calcite was higher after 28 days of
curing than 7 days, suggesting that in the former case gaylus-
site represented the main carbonate phase. Differently, the
samples cured in the carbonation chamber at 50 °C were
mainly characterized by peaks associated to calcite rather
than gaylussite, in agreement with DTG results. Gaylussite is
considered a transient phase in sodium-carbonate activated
slag binders, forming initially but then being consumed in
relation to the development of more stable carbonates, such
as calcite [41]. The fact that calcite was retrieved prevalently
in samples cured in the carbonation chamber at 50 °C may
be related to the enhancing effect of temperature on cal-
cite precipitation. Furthermore, the results of a recent study
indicate that the combination of a higher dosage of sodium
carbonate and laboratory curing at 20 °C could slow down
or limit the dissolution process of gaylussite, some of which
could still remain in the hardened binder matrix even after
28 days of curing [42]; this may explain why gaylussite was
found in samples cured at 20 °C and in particular in those
cured under a ­CO2-rich atmosphere.

13
Waste and Biomass Valorization (2020) 11:3007–3020 3017

CO2 Uptake Mechanical Strength of Slag Mortars

Figure 6 reports the ­CO2 uptake of the tested slag pastes
obtained after curing at different times and activation con-
ditions. It can be observed that the degree of carbonation
of the BOF samples activated with both alkali solutions
showed to increase linearly with curing time in the HC, with
a maximum C ­ O2 uptake around 4% after 28 days. Upon C ­ O2
curing, the C ­ O2 uptake values showed to slightly increase,
regardless of the temperature applied, with respect to those
retrieved in the HC. In particular, the maximum C ­ O2 seques-
tration achieved for the BOF samples mixed with the sodium
hydroxide/sodium silicate solution resulted equal to 5.2%,
when cured in the carbonation chamber at 20 °C. Similarly,
for the sodium hydroxide/sodium carbonate solution, a
maximum uptake of 6% by wt was reached after 28 days of
curing in the carbonation chamber, at both tested tempera-
tures. It is interesting to notice that the samples mixed with
both of the alkali solutions and cured in the carbonation
chamber at 50 °C showed a constant trend with curing time,
Figure 7 reports the compressive strength measured for the
BOF slag mortars obtained using different alkali activators
after 28 days of curing performed at different operating
conditions.
The mortar specimen prepared with the sodium hydrox-
ide/sodium carbonate solution and cured in the carbonation
chamber at 20 °C was characterized by negligible compres-
sive strength even after 28 days of curing. The compressive
strength of the same mortar type cured in the carbonation
chamber at 50 °C increased to around 1 MPa after 28 days
of curing. A similar value was measured for the samples
obtained using the sodium hydroxide/sodium silicate activa-
tor, but curing the mortars at lower temperature, i.e. 20 °C.
On the other hand, with this latter activator, increasing the
3

in agreement with the DTG plot for the peaks associated to SC_CC20

calcite. This may be due to the early formation of carbon- SC_CC50

ates at the outer layer of the specimens that may limit the SS_CC20
Compressive strength (MPa)

further diffusion of C ­ O2 into the core of the slag pastes, thus 2

SS_CC50
hindering further carbonation of the sample. Moreover, in
both cases, only the value achieved after 3 days of curing
resulted higher than that obtained after ­CO2 curing at 20 °C,
likely due to an initial enhancement of the dissolution rate of 1
the reactive minerals (e.g. silicates) at higher temperature.
Indeed, increasing the temperature of the reaction leads to
two opposite effects on the carbonation reaction: on the one
hand, it favours the dissolution of Ca from the solid, while 0
on the other one, it reduces the solubility of ­CO2 [43]. Nev- 3 7 28

ertheless, Liu et al. [44] found that at atmospheric pressure Curing me (d)

the second effect becomes relevant only when carbonation

is carried out at temperatures above 60 °C. Fig. 7  Compressive strength of alkali activated BOF slag mortars,
activated with the corresponding sodium hydroxide/sodium silicate
(SS) and sodium hydroxide/sodium carbonate (SC) solutions, after 28
days of curing in the carbonation chamber at 20 °C (CC20) or 50 °C
(CC50)

Fig. 6  CO2 uptake with curing

8 (a) 8 (b)
time of BOF pastes mixed with
a the SS solution and b SC
solution, cured in the humid- 6 6
CO2 uptake (%)

CO2 uptake (%)

ity chamber (HC), carbonation

chamber at 20 °C (CC20) or at 4 4
50 °C (CC50)
2 2

0 0
0 7 14 21 28 0 7 14 21 28
Curing me (days) Curing me (days)
HC CC20 CC50

13

3018
curing temperature up to 50 °C allowed to obtain a strength
of almost 2 MPa already after 7 days of curing.
The higher strength achieved after activation with the
sodium hydroxide/sodium silicate solution was probably
related to the formation of a C–A–S–H like phase, also
confirmed by the DTG analysis. This finding is in accord-
ance with the results achieved in the work of Puertas and
Torres-Carrasco [45] on BFS, which reported that at set cur-
ing conditions, the highest strength values were obtained for
the samples prepared with a solution of sodium hydroxide/
sodium silicate rather than sodium carbonate. The authors
associated this result to the formation of a more condensed
structure and to a lower porosity of the material, due to the
presence of a C–A–S–H phase.
MIP of Slag Mortars
Figure 8 reports the distribution of the pore volume as a
function of the pore diameter obtained from MIP analysis
carried out on the BOF slag mortars after 28 days of curing.
The lowest cumulative intrusion curve was measured for
the BOF slag mortar, activated with the sodium hydroxide/
sodium silicate solution and cured at 50 °C (SS_CC50), sug-
gesting that this sample was characterized by a lower poros-
ity and hence a much denser pore structure, with respect to
the other samples. The BOF slag mortar obtained using the
same alkaline solution but cured at 20 °C (SS_CC20) was
characterized by a much higher cumulative intrusion, sug-
gesting an increase of the volume of the pores and hence a
higher porosity of the sample. The mortar activated with
the sodium hydroxide/sodium carbonate solution cured at
50 °C (SC_CC50) showed a higher porosity, although pre-
senting a lower amount of macro-pores, with respect to the
one prepared with the SS activator and cured at the same
0,2
BOF100_SS_CC20
BOF100_SS_CC50
Cumulave Intrusion (ml/g)
0,15
BOF100_SC_CC50
0,1
0,05
0
0,001 0,01 0,1 1 10 100 1000
Pore diameter (µm)
Fig. 8  Cumulative pore size distribution, determined by MIP, of
alkali activated BOF slag mortars, activated with the corresponding
sodium hydroxide/sodium silicate (SS) and sodium hydroxide/sodium
carbonate (SC) solutions and cured in the carbonation chamber at
20 °C (CC20) or 50 °C (CC50)
13
Waste and Biomass Valorization (2020) 11:3007–3020
temperature. As reported in the Methods section, the sam-
ples were dried at 40 °C therefore residual moisture presence
that may have interfered with the MIP analysis cannot be
excluded. Nevertheless, it is worth noting that the cumula-
tive intrusion curves obtained for the BOF mortars were
consistent with compressive strength results, confirming
the inverse correlation between porosity and mechanical
strength, also reported in many previous literature studies
(e.g.: [38, 45]).
Conclusions
The experimental study described in this paper was aimed
at assessing the effects of the combination of alkali activa-
tion and C­ O2 curing as a treatment to enhance the hydraulic
behaviour of BOF slag so to allow the reuse of this industrial
by-product in civil engineering applications. The prelimi-
nary isothermal calorimetric study showed that, indeed com-
pared to materials rich in amorphous phases such as BFS,
crystalline residues such as BOF slag are difficult to activate
in terms of pozzolanic behaviour. However, it was possible
to select alkali activator mixtures that allowed to result in
some cumulative heat indicating the formation of hydration
products, i.e. NaOH 2 M/Na2SiO3 50:50 and NaOH (4 M)/
Na2CO3 (2 M) 75:25.
Long term reactivity tests carried out on BOF samples
mixed with these alkali solutions indicated the formation
of a calcium silicate hydrate-like phase particularly in the
samples activated with the sodium hydroxide/sodium silicate
solution. Formation of gaylussite was observed in the sam-
ples activated with the sodium hydroxide/sodium carbonate
solution cured in the humidity or the carbonation chamber
at room temperature. In terms of ­CO2 uptake due (mostly) to
calcium carbonate formation, the maximum value (6%) was
achieved for the BOF slag samples mixed with the sodium
hydroxide/sodium carbonate solution after 28 days of curing
in the carbonation chamber, regardless of the temperature
adopted. As for the overall potential effect of this type of
treatment in terms of ­CO2 sequestration, considering that
based on current data of the World Steel Association glob-
ally around 150 Mton of BOF slag are generated of which
roughly 25% are not reused internally or externally of the
production site, around 2.25 Mton ­CO2 could be stored
annually if all landfilled or stockpiled slag presented the
maximum reactivity found in this work. This number implies
that this type of treatment should be seen more as a waste
valorization strategy rather than a ­CO2 storage one, which
would anyhow be an additional benefit of the process.
As for the results achieved for the mortar samples, acti-
vation with the sodium hydroxide/sodium silicate solution
and curing in the carbonation chamber at 50 °C allowed
to achieve the highest mechanical strength equal to 2 MPa,
Waste and Biomass Valorization (2020) 11:3007–3020 3019
that can be considered suitable for using the products as
non-structural components in civil engineering applications,
such as blinding concrete or fillers. This result is in agree-
ment with the lower porosity and hence denser pore structure
noticed for this sample from mercury porosimetry analysis.
Hence, alkali activation followed by ­CO2 curing, resulted
a feasible route in view of BOF valorization especially using
a sodium hydroxide/sodium silicate solution and perform-
ing the curing post-treatment at relatively high temperature.
The combined process allowed to accelerate the hydration
reactions of the slag and to promote C ­ O2 storage. Further
investigation is anyhow needed for the scale up of the pro-
posed combined process such as an assessment of its costs
also in relation to the type and value of the product that may
be achieved, as well as of environmental impacts related
to potential leaching of metals, metalloids and anions. A
possible increase in the environmental sustainability of this
process, that may be evaluated for example by life cycle
assessment, is the use of alkali solutions from recycled waste
streams (e.g. glass waste, gasification bottom ash or not val-
orized BFS) as a source of silicates instead of natural ores.
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