Cement and Concrete Research 120 (2019) 267–278

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Cement and Concrete Research

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

An initial study on alkali activated limestone binders T

a a b
Dulce Esmeralda Ortega-Zavala , José Luis Santana-Carrillo , Oswaldo Burciaga-Díaz ,
J. Ivan Escalante-Garcíaa,
⁎

a
Centre for Research and Advanced Studies, Campus Saltillo, Mexico
b
Instituto Tecnológico de Saltillo, Saltillo, Mexico

ARTICLE INFO ABSTRACT

Keywords: Alkaline cements were studied using limestone as the only precursor activated with solutions of sodium hy-
Alkali activated cement droxide and waterglass; the activator was used at concentrations of 7 and 10%Na2O using modules of Ms = 0, 1
Limestone binders and 1.5. The compressive strength was followed on pastes and mortars for up to 360 days after an initial curing
CaCO3 at 60 °C for 24 h. A paste with 7%Na2O and Ms = 1.5 and a mortar with 10%Na2O and Ms = 1 reached strength
Characterization
of 15-25 MPa after 360 days; the mortars showed trends towards higher strength with time. The characterization
Hydration products
by SEM, EDS, XRD, FTIR indicated that the microstructure consisted of a mixture of silica gel, carbonates, C-S-H,
Microstructure
N-C-S-H and N-S-H. 29Si MAS-NMR showed the formation of calcium silicates possibly of long chains which
contributed to the strength.

1. Introduction low alkalinity [12–14]. On the other hand, precursors rich in Si + Al

Portland cement (PC) is currently the most used binder and the
industry is a great contributor of gas emissions with more than 8% of
the anthropogenic CO2 [1]. The growing demand for PC must be ad-
dressed with sustainable criteria, among which alternative green ce-
ments is a most prominent route; these include the use of various
supplementary cementitious materials to replace PC, which include
calcined clays, urban wastes, industrial by products and natural re-
sources, as well as others. Partial replacement of PC has been addressed
for decades, while full replacement in the form of alkali activated ce-
ments (AAC), among other alternative cements, has been the subject of
research in the recent decades [2,3].
AAC are commonly prepared using silicoaluminate precursors, such
as calcined clay or pulverized fly ash (PFA) [4–6], which result in
mechanically strong binders [7,8]. Although the properties of the AAC
depend greatly on the chemical and physical features of the precursors,
the chemical processes are somewhat similar among them. Glukhovsky
[9] proposed a model to describe the mechanisms that regulate the
alkaline activation of silicoaluminates in three stages: dissolution/hy-
drolysis; reorganization and condensation of species and lastly poly-
condensation [10].
Among the various AAC Palomo et al. [11] proposed two models of
reaction products depending on the composition of the precursors. On
the one hand, precursors rich in Si + Ca (e.g. blast furnace slag), form
C-S-H as the main reaction product after activation using solutions of
(e.g. metakaolin and fly ash, of SiO2/Al2O3 ratios between 1 and 2)
[15,16] and low Ca contents, to obtain inorganic polymers of N-A-S-H
of high mechanical strength [17,18]. The resulting properties are in-
teresting from various perspectives, such as high strength [19,20],
chemical resistance to sulfates and sea water [21,22], durability in
acidic media [23–25] and resistance to chloride penetration [26,27].
One requirement for precursors of AAC is the presence of an
amorphous or glassy fraction to be susceptible to the alkaline attack
[28,29]; the higher the glassy fraction, the more reactive the precursor,
although it also depends on other factors such as the surface area,
temperature, etc. Some precursors possess a high content of amorphous
fraction as generated in their origin, such as PFA; while others require
rapid cooling, as the blast furnace slag, or firing at T ≥ 600 °C to disrupt
the crystalline structural order, such as metakaolin or rice husk ash.
Blast furnace slag requires a mechanical activation (milling) to be used
as a precursor, which for a Blaine of 498 m2/kg consumes about
47.2 kW h/ton; on the other hand, a widely available precursor such as
limestone requires less than half of the energy consumed by the slag for
grinding at similar levels of surface area (20.1 kW h/ton) [30]. Thermal
or mechanical conditioning (activation) of the precursors tend to in-
crease costs and consumption of natural resources.
The use of precursors that are widely available, abundant, cheap
and with no requirements of thermal treatment is of interest. Such
seems to be the case of limestone (LS) as an alternative precursor to
prepare AAC. Limestone is a sedimentary rock that occupies ~15% of

⁎
Corresponding author.
E-mail address: ivan.escalante@cinvestav.edu.mx (J.I. Escalante-García).

https://doi.org/10.1016/j.cemconres.2019.04.002
Received 26 November 2018; Received in revised form 12 March 2019; Accepted 1 April 2019
0008-8846/ © 2019 Published by Elsevier Ltd.
D.E. Ortega-Zavala, et al.
the earth crust [31] and it represents about 80% of the raw materials
used to produce PC. LS is used to replace PC in about 10% as in inert
addition in agreement with EN 197-1 [32]; up to 35% replacement of
PC by LS is also allowed in some instances [33,34]. On the other hand,
the use of LS in AAC has been reported in combination with PC-fly ash
[35], waste urban glass [36] and blast furnace slag [37]; LS has been
reported to improve the mechanical properties and to take place in the
chemical reactions contributing with Ca2+ ions to form strong reaction
products [38]. Gao et al. [39] studied blends of fly ash, blast furnace
slag and LS activated with sodium hydroxide and sodium silicates, they
pointed that the reaction processes are enhanced by the LS that per-
formed as nucleation sites; nonetheless, the process is controlled by the
slag.
In general terms, there is uncertainty as to the role of the LS in the
alkaline cements and there is not enough information available in the
literature, much less on binders containing 100%LS; two references are
related to this research. A patent [40] described alkali activated lime-
stone concretes, the content of limestone in the binder was 40–100%
combined with metakaolin, blast furnace slag, PC and fly ash, activated
with combinations of nNa2SiO3, Na2CO3, K2CO3, CaO, K2CO3, Ca(OH)2.
Another work reported studies on pastes and mortars using Na2CO3 and
CaCO3 from various origins such as aragonite, limestone, calcite,
marble and dolomite using loads of 20–80 wt% of alkaline and earth
alkaline carbonates [41]. Nonetheless, neither of the two referred works
showed evidence of success with the use of LS as the only precursor. A
report on binders based on calcium carbonates [42] used three different
calcium carbonate rocks; the rock with %MgO = 19.7 resulted in 28-
day strength of 40.48 MPa after permanent curing at 40 °C; however,
the authors did not show details regarding the alkaline activator other
than they used waterglass as the activator.
Considering the above, this paper presents initial results on the use
of LS as the only precursor to prepare alkali activated cements using
sodium silicate solutions. Pastes and mortars were prepared and char-
acterized for up to 360 days curing in terms of mechanical properties,
composition and structure of the reaction products as well as the mi-
crostructural evolution.
2. Experimental
2.1. Materials
2.1.1. Precursor
Pastes and mortars were prepared using a local commercial lime-
stone sand (LS) with a maximum particle size of ¼ inch and a density of
2540 kg/m3 with a pale gray physical appearance. The LS was ball
milled to a Blaine surface area of 600 m2/kg [43], the chemical com-
position by X-ray fluorescence was (wt%) 57.43 CaO, 1.06 SiO2 and
41.51 loss on ignition; the X-ray diffraction pattern of the LS showed
only peaks of calcite as the main crystalline phase.
2.1.2. Alkaline activators
The alkaline activator solutions were prepared using purified water
and industrial grade waterglass of modulus (Ms = SiO2/Na2O molar
ratio) of 2.96 and flakes of sodium hydroxide; their chemical compo-
sitions are given in Table 1. The SiO2/Na2O ratio of the alkaline acti-
vator solution was adjusted at 0, 1 and 1.5 by adding NaOH to the
sodium silicate. The alkaline solutions were equilibrated at room tem-
perature for 2 h before their use in the pastes and mortars.
Table 1
Chemical composition of alkaline activators.
Na2O (%wt.) SiO2 (%wt.) H2O (%wt.)
Sodium silicate 9.41 27.81 62.78
NaOH (98% purity) 77.49 – 22.51
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Cement and Concrete Research 120 (2019) 267–278
Table 2
Nomenclature and details of the formulations of the limestone pastes.
No. Nomenclature %Na2O %SiO2/Na2O w/b
1 P-7-0 7 0 0.27
2 P-7-1 7 1 0.27
3 P-7-1.5 7 1.5 0.27
4 P-10-0 10 0 0.27
5 P-10-1 10 1 0.27
6 P-10-1.5 10 1.5 0.36
Reference of silica Reference 10 1 0.30
%Na2O, relative to the mass of limestone.
2.1.3. Aggregate
The same LS described before was used as an aggregate for the
preparation of mortars; it had a maximum particle size of 4.75 mm and
the fineness module was of 2.9. The water absorption (WA) was mea-
sured as 2.78% as per [44].
2.2. Sample preparation
2.2.1. Preparation of pastes
6 pastes of LS were prepared activated with 7 and 10% Na2O and Ms
of 0, 1 and 1.5; Table 2 summarizes the nomenclature and formulation
details. A reference paste was also prepared by using only ground silica
sand (quartz) as a precursor ground to pass the #325 sieve. The water/
binder ratio (w/b, including the water from the solution of the acti-
vator) was adjusted to a preferred workability according to the re-
quirements of each formulation. Batches of 2400 g of LS were blended
in a mixer with orbital movement for 4 min, the pastes were cast into
cubic molds of an alkali resistant polymer of 2.5 cm per side and vi-
brated for 15 s to eliminate entrapped air. The molds were covered with
a plastic film to avoid water losses during the setting that took place for
24 h at 60 °C; afterwards, the specimens were demolded and dry stored
in plastic bags in an isothermal chamber at 20 ± 2 °C, the relative
humidity was within the range 80–90%.
2.2.2. Preparation of mortars
The mortars were prepared for each of the pastes described above,
using an aggregate:binder mass ratio of 3:1 in batches of 3200 g. The
sand was pre-saturated with water before blending it with the paste, so
it would not absorb the alkaline solution. The mortars were mixed for
4 min and casted into the same molds described above in two stages,
these were half filled and vibrated for 15 s, then completely filled and
vibrated for 10 s more. The curing conditions were the same as de-
scribed for the pastes.
2.3. Characterization
The specimens of pastes and mortars were cured for up to 360 days
at 20 °C. For each formulation and curing age, 4 specimens were ran-
domly taken for mechanical testing in a hydraulic press with a loading
speed of 200 N/s and sensitivity of 0.5 kN. Fragments of the crushed
cubes were immersed in methanol for 72 h and then dried in a vacuum
oven for 72 h at 36 °C. Some dried fragments of pastes samples were
ground in a planetary mill, using agate media, at 300 rpm to pass the
#140 sieve; these were used for various characterization techniques
described as follows. The phases evolution was followed by X-ray dif-
fraction (XRD, X'Pert 3040, Phillips) using Cu Kα radiation at 40 kV and
30 mA, the range was 10–80°2θ, with a step of 0.03°2θ every 3 s. The
functional groups of the reaction products were studied by Fourier
transformed infrared spectroscopy (FTIR, Frontier FT-IR/NIR, Pike
Technologies); the frequencies ranged from 4000 to 450 cm−1, using
200 scans and a spectral resolution of 4 cm−1. 29Si MAS-MNR, Magic-
Angle Spinning Nuclear Magnetic Resonance, (Bruker Avance II 300
NMR) was used at a frequency of 59.63 MHz applying 5 kHz spinning
D.E. Ortega-Zavala, et al.
rate on a 4 mm CP-MAS probe using zirconia rotors. Single pulse ex-
periments were carried out by applying 90° pulses of 4.0 μs with CW 1H
decoupling field strength of 35.0 kHz, and recycle delays of 10 s. The
29
Si chemical shift of the acquired spectra was referenced externally to
tetramethylsilane [Si(CH3)4] at 0.0 ppm. The deconvolutions of the 29Si
MAS spectra were performed by the Gauss-Lorentz adjustment curve of
the DMFIT freeware [45].
The microstructure of pastes and mortars was studied by scanning
electron microscopy (SEM, XL-30 ESEM, Phillips) accessorized with
energy dispersive spectroscopy (EDS) for spot analysis of the chemical
composition. The specimens were obtained from cubic samples that
were not subjected to mechanical testing, although these were crushed
with a hammer to obtain fragments that were vacuum dried and further
embedded in slow setting epoxy resin and polished with a series of SiC
paper of numbers from 320 to 1000 and diamond pastes of 3 and
1.5 μm. Methanol was used as a lubricant to avoid the presence of
water. The samples were coated with graphite for observation under the
SEM and representative backscattered electron images were taken at
1000 and 2000 magnifications. The operation conditions were of
25 keV and a working distance of 7 to 7.6 mm. To complement the
characterization, 30 EDS spot analysis were taken from each sample to
obtain a representative estimation of the chemical composition of the
condensed reaction products.
3. Results and discussion
3.1. Compressive strength (CS)
Fig. 1 shows the compressive strength evolution from 1 to 360 days
for the limestone pastes and mortars. The variation of the %Na2O did
not show a clear pattern for pastes and mortars; on the other hand, and
for any given %Na2O, a Ms ≥ 1 was favorable and the strength in-
creased over time. A synergistic effect among the %Na2O and Ms was
not evident.
For the pastes activated with 7% Na2O, the highest strength at
360 days was for paste P-7-1.5 with Ms = 1.5, reaching 24 ± 2.28 MPa
and showing a positive trend; while the use of 10% Na2O and Ms = 0
resulted in 8 ± 1.34 MPa for up to one year. This was probably due to
the recrystallization of LS; it is possible that the alkaline media dis-
solved the structure of the LS, and Ca2+ ions that carbonated with at-
mospheric CO2 and densified the matrix favoring the strength; this is in
agreement with a report of dissolution of LS in alkaline solutions, that
Fig. 1. Compressive strength versus curing time of limestone (a) pastes and (b) mortars.
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Cement and Concrete Research 120 (2019) 267–278
concluded that the NaOH showed higher dissolution of Ca from LS than
Na2CO3 and Na2CO3/NaOH [36].
A strength reduction was noted for the paste with 10% Na2O and
Ms = 1 after 180 days, which could be related to two possible phe-
nomena: on the one hand, an increased pH in the presence of humidity
limits the solubility of the Ca [46], so any unreacted Na provided by the
alkaline solution tends to carbonate; on the other hand, an excess of
alkalis can lead to deleterious carbonation processes [47,48]. Alkali
carbonates have a larger volume than that initially occupied by water
and when dry, these generate internal stresses and deterioration of the
cement pastes in detriment of the compressive strength.
It is noteworthy that the reference sample did not properly set and
did not keep the shape of the cubic mold so these could not be me-
chanically tested, while the binders prepared with LS set and hardened
properly preserving their dimensional stability, as shown in Fig. 2; the
ground quartz sand used as a reference precursor was inert to the
conditions of alkaline activation as the reported in geopolymeric bin-
ders [49] and did not even promote the condensation of the waterglass.
This is an indicator of the involvement of the LS in the chemical reac-
tions.
On other hand, the strength of mortars increased slightly with the %
Na2O, the highest 360 days strength was for the mortar M-10-1
(Fig. 1b). The mortars with Ms ≥ 1 showed steady strength gain with
positive slopes even after 1 year; these did not show strength losses as in
the pastes, this could be related to the fine particles from the sand, that
could have also performed as a precursor in spite of their larger particle
size compared to the ground limestone; this in turn would consume
alkalis and reduce their potential deleterious carbonation. An addi-
tional effect could be as that pointed by Rakhimova et al. [50], in that
the LS containing more than 39% of particles with a size lower than
5 μm provides nucleation sites and accelerates the reaction process of
blended alkali-activated cements reinforcing the microstructures. Un-
like the pastes, mortars with SiO2/Na2O = 0 developed strength lower
than 2 MPa for 7 and 10% Na2O, it appears that under these conditions,
the alkaline solution did not provide an adequate environment to in-
duce the reaction of the LS (precursor and aggregate) for the formation
of cementitious products, therefore the presence of silica species pro-
vided by the addition of sodium silicate seems to be essential for de-
veloping the compressive strength.
It is noteworthy that pastes and mortars reached similar strengths
after 1 year; the mortars activated with a solution of SiO2/Na2O > 0
showed a clear trend towards higher strengths over time. The mortars
D.E. Ortega-Zavala, et al. Cement and Concrete Research 120 (2019) 267–278

Fig. 2. Photographs of specimens prepared with ground silica sand as reference and with limestone.

Fig. 3. X-ray diffraction patterns for selected pastes at different ages.

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D.E. Ortega-Zavala, et al. Cement and Concrete Research 120 (2019) 267–278

have an advantage as less alkaline solution is required for a given mass Table 3
of matter, reducing costs and the risk of carbonation. Bands on the FTIR spectra of the activated limestone pastes.
Band cm−1 Attribution
3.2. X-ray diffraction (XRD)
1 686 Si-O-Si [57]
2 712 C–O (CO32−) [54,58]
Four pastes with high and low strength were characterized for up to 3 863–872 C–O (CO32−) [44,53]
360 days by XRD, the results are shown in Fig. 3, which includes the LS 4 901 Si-O [59]
as reference. After 1 day, thermonatrite (Na2CO3·H2O, PDF 01-72-578) 5 975–1006 v3(Si-O) C-S-H [57,60,61]
6 1069 T-O (T]Si, Al) [62]
was observed in pastes P-7-1 and P-7-1.5 (Fig. 3a); for Ms = 1, the
7 1395–1408 C-O (thermonatrite) [63,59]
reflections increased with time, while, the contrary was noted from 8 1428 C–O (CO32−) [53]
28 days onwards for Ms = 1.5. For the paste that showed strength losses 9 2515 C-O [60]
after 180 days (P-10-1), the XRD patterns also showed reflections of
thermonatrite whose intensity reduced over time. The patterns of the
paste P-10-0 in Fig. 3b showed reflections of pirssonite (Ca- 3.3. FTIR
Na2(CO3)2(H2O)2, PDF 01-70-2405) and portlandite (Ca(OH)2, PDF 44-
1481), which evidenced that the limestone dissolved under the alkaline The pastes with highest strength (P-7-1 and P-7-1.5) were analyzed
environment as can be noted by the reduced intensity of the CaCO3 by FTIR after 1, 28, 180 and 360 days, the results are shown in Fig. 4
peaks with respect to the XRD pattern of the LS; Avila-López et al. [36] (including the spectrum of the unreacted limestone); Table 3 list the
reported that the alkaline activation of waste glass and limestone band assignments for the spectra. Bands 2, 3, 8 and 9 were ascribed to
formed pirssonite in binders activated with NaOH (Ms = 0). It appears the O-C-O bond from the limestone precursor [53,54]; after the alkaline
that the interaction of NaOH-limestone forms Ca(OH)2, and both hy- activation, band 9 was less evident as time advanced which points to-
droxides carbonated readily with CO2. The formation of thermonatrite wards the participation of the limestone in the reactions. One band
and pirssonite suggest two possible effects on the binders micro- more between 1395 and 1408 cm−1 (band 7) was detected in P-7-1.5, it
structure: (1) the carbonates can reduce the porosity densifying the corresponds to stretching vibrations of CO, confirming the presence of
matrix (P-7-1 and P-7-1.5) benefiting the compressive strength; how- carbonate groups incorporated after the alkaline activation [55,56],
ever, (2) these carbonates occupy a greater volume than the original which was very close to the band 8 noted in the unreacted limestone;
hydroxides, which in presence of moisture would generate internal the formation of carbonates after exposure to atmospheric air [54] was
stresses and strength losses in the pastes (P-10-0 and P-10-1). supported by the XRD results (Fig. 4b).
The identification of characteristic reflections of C-S-H, which is a For paste P-7-1.5, sodium carbonates or NaOH were not observed by
main cementitious phase reported in alkali activated cements, based on XRD or FTIR (band 7), an explanation to this phenomenon, in agree-
Ca rich precursors, and in PC based materials [51,52] was complicated ment with another investigation [61], is that Ca could have redis-
due to its low crystallinity and by the overshadowing by the intense tributed on the surface of N–S–H gels to satisfy surface charges or in the
peaks of calcite (PDF 5-586); however, its formation can be elucidated C–S–H. Sodium silicate gels N-S-H tended to form under the influence of
from other characterization techniques discussed later. increased %Na2O, which also possibly modified the degree of

Fig. 4. FTIR spectra of alkali-activated limestone for 1, 28, 180 and 360 days. (a) Paste P-7-1 and (b) Paste P-7-1.5.

271
D.E. Ortega-Zavala, et al.
29
Fig. 5. Si MAS NMR spectra for 360 days pastes.
polymerization of the C–S–H, as shown below in the NMR spectra. In
either case, new gel surfaces are likely to provide the necessary sites for
cation adsorption.
The bands 1 and 6 were attributed to the bending vibrations Si-O-Si
[64] and T-O (T]Si, Al) [62] bonds respectively; while band 4 was
associated with SieO bonds [65]; these signals suggest the condensa-
tion of the alkaline activator of waterglass forming silica gel which also
contributes favorably to the mechanical strength. The absorption bands
5 located at around 975 and 1006 cm−1 have been attributed to the
stretching vibrations in the SieO bonds (v3(SieO)) in the SiO4 tetra-
hedra in C-S-H in the form of Q2 units [55–56,65]. The frequency of
band 5 is directly related to the alkaline activator; lower frequencies
appear after activation with NaOH and higher frequencies appear after
the activation with waterglass or Na2CO3 [66]. It is noteworthy that
band 5 became more intense with increasing the Ms of the alkaline
activator; this would agree with the higher strength results of the pastes
with Ms = 1.5 that increased for up to 360 days. The spectra also
showed that increased Ms shifted the position of band 5, from 981 cm−1
for Paste P-7-1 with Ms = 1 to 1006 cm−1 for paste P-7-1-5 with
Ms = 1.5, which suggests structural and compositional differences
among the C-S-H formed in both systems.
29
3.4. Si MAS-NMR
The 29Si MAS NMR spectra for the pastes P-7-1 and P-7-1.5 after
360 days are presented in Fig. 5. The signals were classified as Qn,
where “Q” represent the Si atom which is bonded to four oxygens and
“n” (n = 0,1,2,3,4) is the number of bridging oxygens [67–69]. The
colored bands correspond to the chemical shifts ranges assigned ac-
cording to Engelhardt [68].
The NMR spectra for the pastes showed broad peaks within the
region of Q2 and Q3; the most intense of Q2 centered at about
−88.58 ppm for paste P-7-1 (Fig. 5a), whereas for paste P-7-1.5 the
strongest signal appeared as two peaks of Q2 and Q3 at −91.46 and-
94.9 ppm, respectively. The spectra also show signals in the regions Q4
and the broad Q2 peaks suggest that weak signals from Q1 peaks are
also underlying. Interestingly, the spectrum of the paste of Ms = 1 is
like what is seen in low Ca cements that form tobermorite-like C-S-H,
having very long silica chains constituted mostly by Q2 and very little
Q1; on the other hand, the strong signals Q3 and Q4 indicate the con-
densation of silica gel from the alkaline solution. The increased in-
tensity of the Q3 signals for the paste of Ms = 1.5, suggests that the
waterglass of higher Ms participated in the formation of more complex
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Cement and Concrete Research 120 (2019) 267–278
structures also condensing as a silica gel, although heavily disrupted,
which appeared to have favored the mechanical strength.
3.5. Microstructural characterization
Pastes and mortars with the highest 360 days compressive strength
were characterized by SEM in terms of the microstructure and the
chemical composition of reactions products.
3.5.1. Microstructures
Fig. 6 shows the microstructures of polished samples of selected
pastes aged for 28 and 360 days. The reaction products in pastes P-7-1
and P-7-1.5 formed similar matrixes of reaction products, which den-
sified over time increasing the strength. It appears that after 360 days
for both binders, the amount of unreacted LS particles decreased, sug-
gesting its participation in the reaction process. The spot analyzes by
EDS, taken as far as possible from the LS particles in order to avoid their
inclusion in the measurement of the chemical composition, indicated
high contents of Si and Ca, which suggests the precipitation of silica gel
and calcium silicate hydrates, as discussed above. The Na signal on the
EDS from the matrix could result from its incorporation in the silica gel
(N-S-H), in sodium carbonates, in the calcium silicates [70,71] or in the
form of fine intermixes of such compounds. A previous report [72]
suggested that the calcium silicates gels (C-S-H) could incorporate al-
kaline cations to its chains; in some cases, the sodium amount is higher
enough so the modification is named N-C-S-H gel [70,71].
Cracks were noted for pastes activated with higher Ms, these could
have various origins, namely, from the crushing of the specimens to
obtain fragments, from the vacuum drying (of the condensed silica gel)
of the fragments to eliminate free water for the reactions, from the
polishing process and/or from the drying (of the condensed silica gel)
under the vacuum within the SEM column [47].
The microstructures of mortars of compositions M-10-1 and M-10-
1.5 cured for 28 and 360 days are shown in Fig. 7. As noted for the
pastes, the matrices of reaction products were similar, comprised of
unreacted limestone particles, a dense matrix of reaction products and
pores. After 360 days, the reaction products precipitated in gray dense
zones (labeled G1), this was more evident in the mortar with Ms = 1.
The fast-initial reaction of LS with alkaline solution limited the time for
diffusion of species, so high concentration of reaction products built up
in the silica gel zone leaving also coarse porosity in other areas. As the
limestone dissolution continues, Na is incorporated in the C-S-H chains,
or precipitates within pores as carbonates or forms calcium-modified
D.E. Ortega-Zavala, et al.
Fig. 6. Microstructures and chemical composition of pastes P-7-1 and P-7-1.5 after 28 and 360 days, scanning electron microscopy by backscattered electron.
silica phase in the volume originally occupied by silica gel. Thus, re-
action products as N-C-S-H, C-S-H and N-S-H seem to be responsible for
the strength as time passes.
Fig. 8 shows elemental X-ray maps of Si, Na and Ca corresponding to
a zone similar to that labeled as G1 in Fig. 7 from mortar M-10-1 (10%
N2O, Ms = 1) after 360 days. The distribution of the reaction products
formed a matrix with some dispersion of Si, Ca, and Na. The individual
maps allow the identification of different components in the micro-
structure, e.g. the LS particles are readily identified from the Ca map,
which show absence of elements in the Na and Si maps.
A slight mismatch can be noted among the areas in the maps and
those in the microstructure, which could originate from the differences
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Cement and Concrete Research 120 (2019) 267–278
of depth of origin from the surface of the specimen; i.e. the secondary
imaging electrons come from 1 to 10 nm while the X-ray signals come
from a depth of 0.2–2 μm [73].
The maps of Si, Ca and Na show that these elements distributed
throughout the matrix, in agreement with the results discussed above.
Image manipulation allowed to combine and overlap the 3 elemental
maps (see Fig. 8), from which various zones can be identified and la-
beled as:
• Zone A: showing only Ca + Na, indicate areas of formation of so-
dium/calcium carbonate (identified by XRD).
• Zone B: showing only Si, shows condensed silica gel
D.E. Ortega-Zavala, et al.
Fig. 7. Microstructures and chemical composition of mortars M-10-1 and M-10-1.5 after 28 and 360 days, scanning electron microscopy by backscattered electron.
• Zone C: showing Si + Na indicates areas of formation of silica gel
modified with Na (N-S-H).
• Zone D: showing only Ca + Si, points to the identification of C-S-H,
which seems relatively abundant and distributed throughout the
matrix of reaction products.
• Zone E: showing the presence of Ca + Si + Na, evidenced the in-
corporation of Na+ into the C-S-H (N-C-S-H), which was relatively
abundant.
The matrix appears to be a mixture, where the calcium silicate
predominates (C-S-H and N-C-S-H) and are finely intermixed with
carbonates and silica gel (SeH and N-S-H) that condensed from the
unreacted waterglass.
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Cement and Concrete Research 120 (2019) 267–278
3.5.2. Chemical composition of reaction products
Fig. 9 presents the energy dispersive X-ray spectroscopy (EDS) re-
sults from 30 spot analyses per specimen, these were taken throughout
the matrix of reaction products from selected pastes (P-7-1 and P-7-1.5)
and mortars (M-10-1 and M-10-1.5) after curing for 360 days. The
composition of the reaction products was plotted in ternary diagrams of
atomic percentages of Ca-Si-Na; the composition of LS was included as a
reference, which takes the apex of Ca. The average atomic rations are
presented in Table 4.
For the pastes, the composition of the reaction products formed
clusters with some dispersion along the CaeSi composition with low Na
contents, the dispersion could indicate two possible configuration of
phases: (1) the formation of reaction products that consisted of a fine
D.E. Ortega-Zavala, et al. Cement and Concrete Research 120 (2019) 267–278

Fig. 8. Overlapping of Ca, Si and Na maps; image manipulation of Elemental X-ray maps of the mortar M-10-1 (10%Na2O, Ms = 1) after 360 days.

Fig. 9. Chemical composition in % at. of reaction products of select pastes and mortars after 360 days.

275
D.E. Ortega-Zavala, et al. Cement and Concrete Research 120 (2019) 267–278

Table 4
Average atomic ratios of reaction products by EDS at 360 days.
% atomic (s.d. = standard deviation)

Sample Ca Si Na Ca/Si Si/Na Na/Ca

Paste P-7-1 47.98 (4.65) 22.72 (5.48) 29.29 (4.43) 2.11 0.77 0.61
Paste P-7-1.5 45.13 (2.9) 42.701 (3.33) 12.16 (1.88) 1.05 3.51 0.28
Mortar M-10-1 67.35 (1.86) 24.37 (1.37) 8.27 (1.51) 2.76 2.94 0.12
Mortar M-10-1.5 52.76 (1.98) 39.96 (1.91) 7.27 (1.17) 1.32 5.49 0.13

intermixture of silica gel, carbonates, C-S-H and N-C-S-H; (2) the elec-
tron beam excited volumes contained condensed silica gel (including N-
S-H) from the activator and limestone. However, the mechanical
properties and the rest of the characterization techniques support
configuration 1. When the data cluster plots closer to the Si apex, it
suggested the precipitation of more silica gel in the matrix of reaction
products; on the other hand, the presence of carbonates and very fine
particles of LS intimately mixed in the matrix of reaction products
displaced the data cluster towards the Ca apex.
The composition of the reaction products of paste P-7-1 and mortar
M-10-1 with Ms = 1 showed Ca/Si ratios of 2.11 and 2.78, respectively,
which indicates the possible formation of C-S-H and N-C-S-H; the Ca/Si
ratio influences the ability to incorporate alkalis into the C-S-H struc-
ture; a Ca/Si > 1.5 ratio increases the tendency to bind alkalis into the
C-S-H chains and decreases their availability in the pore solution [74],
the union of the alkaline cation occurs in the silanol sites and is driven
because the acid sites are neutralized by reaction with strong base, ei-
ther NaOH or KOH [70,75].
4. Discussion
Limestone binders activated with waterglass or NaOH represent a
promising binder of very low CO2 emissions, as it does not require any
thermal treatment, as is the case for precursors of calcined clays (e.g.
metakaolin); most of the precursors for alkaline binders require some
kind of grinding, limestone has very low milling energy demands,
which are 57% lower than that of blast furnace slag [30]. Coal fly ash
could be used without any grinding, but the byproduct is not as readily
available world wide as limestone.
The comparative contribution to CO2 from the manufacture of
100 kg of binders of PC and LS can be estimated using data from the
literature, which vary widely, this is summarized in Fig. 10. The ratio of
kg CO2 emissions per kg of PC ranges between 0.82 and 1 [76]; while
the CO2 emissions per kg of NaOH and waterglass are 1.915–3.18
[77,78] and 1.22–1.76 kg, respectively [79,80]. 100 kg of PC would
result in the emission of 82–100 kg of CO2; whereas 100 kg of a LS
binder activated with 10%Na2O and Ms = 1 would emit 71–90 kg CO2.
The use of other sources of alkali activators could further reduce the
CO2 emissions. Also, alkali activated Limestone binders demand much
less water than PC binders without the need of superplasticizers (which
also contribute to cost and CO2 emissions with 0.0749 kg CO2 eq [80]).
Also, the production of PC involves grinding of raw materials and
clinker, while for LS only one operation is needed.
The densification of the microstructures and strength gains from 28
and 360 days of curing evidenced a continuous participation of the LS
in the reactions. The densification of the microstructures and strength

Fig. 10. CO2 emissions for 100 kg of LS and PC binders.

276
D.E. Ortega-Zavala, et al.
gains evidenced a continuous participation of the LS in the reactions.
The process seems to start with the hydrolysis and partial dissolution of
the LS particles, leading to the formation of Ca2+ and CO32− ions in
aqueous medium that further reacted with SiOx(OH)4−x−x, Na+ and
OH− from the waterglass [48]. Over time the species became more
complex saturating the aqueous media until form diverse reaction
products (Fig. 3).
After 28 days all of the silicate species from the waterglass must
have already condensed forming dense products (Fig. 6); so the ob-
served densification, and strength gains, indicates further interaction of
the silicates and the limestone. In agreement with the above, it was also
noted that the number and size of LS particles reduced over time,
however all the pastes developed strength slowly which could be a
shortcoming to solve in the further.
The overlapping of the maps of Si, Ca and Na evidenced the pre-
sence of reaction products distributed throughout the matrix in the
mortar M-10-1, which was in agreement with the results from XRD,
SEM, EDS, FTIR and 29Si MAS-NMR; the results suggest the formation of
C-S-H, N-C-S-H, silica gel, N-S-H and carbonates finely intermixed; such
configuration resulted in microstructures that imparted useful me-
chanical properties to the binders. It is suggested that either sodium
silicate gels formed under the influence of increased NaOH concentra-
tions or that C-S-H itself was modified to higher degrees of silicate
polymerization by the effect of NaOH addition; in either case, new gel
surfaces are likely to provide the necessary sites for cation adsorption
(Na+).
5. Conclusions
This paper presents some initial results of a new type of alkaline
binders of low emissions and low cost. Limestone is a cheap and widely
available precursor, so these binders can have a positive impact
wherever Portland cement is produced. The investigation of the com-
position of reaction products, microstructure, structure and compres-
sive strength of alkali activated binders using limestone as the precursor
in pastes and mortars allow the following conclusions:
• limestone of a surface area of 6000 cm /g can be used as a precursor
2 [16] D. Roy, Alkali-activated cements. Opportunities and challenges, Cem. Concr. Res.
to produce alkali activated binders; pastes and mortars rendered
compressive strengths from 15 to 25 MPa after 360 days.
•
The limestone binders are green cements as these eliminate the
thermal treatment and the milling demands considerably less energy
than Portland cement.
• The use of alkaline waterglass solutions of SiO2/Na2O = 1 and 1.5
dissolved the limestone and promoted the formation of carbonates,
such as thermonatrite and pirssonite. A paste activated with 10%
Na2O and Ms = 0 formed portlandite that re‑carbonated favoring
the strength.
• The characterization by X-ray diffraction, infrared spectroscopy,
scanning electron microscopy, energy dispersive spectroscopy and
29
Si MAS-NMR indicated that the reaction products are governed by
the presence of silicate chains that included a finely intermix blend
of C-S-H, N-C-S-H, N-S-H, silica gel and carbonates.
•
The Q2/Q1 ratio obtained from the deconvolution of the 29Si MAS-
NMR spectra for the pastes showed values > 4, which indicated
that the reaction products of the limestone activated with waterglass
were a mixture of calcium silicates of long chains.
Further research is needed to improve the understanding of the
reaction mechanisms and the mechanical properties, as well as in-
vestigations on the reactions during the first 48 h, long term durability
of mortars and concretes, improving the water resistance by means of
using other precursors or binders, etc.
277
Cement and Concrete Research 120 (2019) 267–278
Acknowledgements
Thanks are due to Conacyt México for the scholarship 421374 of
Ortega Zavala and Project 114 of the Fund SEP-Cinvestav 2018.
References
[1] J. Olivier, G. Janssens-Maenhout, M. Muntean, J. Peters, Trends in Global CO2
Emissions: 2016 Report, PBL Netherlands Environmental Assessment Agency, The
Hague, 2016http://edgar.jrc.ec.europa.eu/news_docs/jrc-2016-trends-in-global-
CO2-emissions-2016-report-103425.pdf , Accessed date: 3 November 2019.
[2] F. Pachecho-Togal, J. Castro, S. Jalali, Alkali-activated binders: a review. Part 2.
About materials and binders manufacture, Constr. Build. Mater. 22 (2008)
1315–1322, https://doi.org/10.1016/j.conbuildmat.2007.03.019.
[3] A. Palomo, P. Krivenko, I. García-Lodeiro, E. Kavalerova, O. Maltseva,
A. Fernández-Jiménez, A review on alkaline activation: new analytical perspectives,
Mater. Constr. 64 (2014) 140–159, https://doi.org/10.3989/mc.2014.00314.
[4] F. Slaty, H. Khoury, J. Wastiels, H. Rahier, Characterization of alkali activated
kaolinitic clay, Appl. Clay Sci. 75 (2013) 120–125, https://doi.org/10.1016/j.clay.
2013.02.005.
[5] J.L. Provis, Alkali-activated materials, Cem. Concr. Res. 114 (2018) 40–48, https://
doi.org/10.1016/j.cemconres.2017.02.009.
[6] Z. Pan, Z. Tao, Y.F. Cao, R. Wuhrer, T. Murphy, Compressive strength and micro-
structure of alkali-activated fly ash/slag binders at high temperature, Cem. Concr.
Compos. 86 (2018) 9–18 https://doi.org/10.1016/j.cemconcomp.2017.09.011.
[7] J. Davidovich (1990), Process for obtaining a geopolymeric alumino-silicate and
products thus obtained. US3950470A, 1972.
[8] J. Davidovits, Geopolymers: inorganic polymeric new materials, J. Mater. Educ. 16
(1994) 91–138.
[9] V. Glukhovsky, Soil Silicate Articles and Structures, Budivelnyk Publisher, Kiev,
Ukraine, 1967 (Budivelnyk Publisher).
[10] V.D. Gluchovskij, Gruntosilikaty Gosstrojizdat Kiev. USSR 245 627, (1967).
[11] A. Palomo, M.W. Grutzek, M.T. Blanco, Alkali-activated fly ashes. A cement for the
future, Cem. Concr. Res. 29 (1999) 1323–1329, https://doi.org/10.1016/S0008-
8846(98)00243-9.
[12] A.O. Purdon, The action of alkalis on blast furnace slag, J. Soc. Chem. Ind 59 (9)
(1940) 191–202.
[13] O. Burciaga-Díaz, M.R. Díaz-Guillén, A.F. Fuentes, J.I. Escalante-García, Mortars of
alkali-activated blast furnace slag with high aggregate: binder ratios, Constr. Build.
Mater. 44 (2013) 607–614, https://doi.org/10.1016/j.conbuildmat.2013.03.057.
[14] J.I. Escalante-García, A. Fuentes, A. Gorokhovsky, P. Fraire-Luna, G. Mendoza-
Suarez, Hydration products and reactivity of blast-furnace slag activated by various
alkalis, J. Am. Ceram. Soc. 86 (12) (2004) 2148–2153, https://doi.org/10.1111/j.
1151-2916.2003.tb03623.x.
[15] A. Palomo, S. Alonso, A. Fernández-Jiménez, I. Sobrados, J. Sanz, Alkaline activa-
tion of fly ashes. NMR study of the reaction products, J. Am. Ceram. Soc. 87 (6)
(2008) 1141–1145, https://doi.org/10.1111/j.1551-2916.2004.01141.x.
(1999) 249–254, https://doi.org/10.1016/S0008-8846(98)00093-3.
[17] L. Weng, K. Sagoe-Crentsil, T. Brown, S. Song, Effects of aluminates on the for-
mation of geopolymers, Mater. Sci. Eng. B 117 (2) (2005) 163–168, https://doi.org/
10.1016/j.mseb.2004.11.008.
[18] A. Fernández-Jiménez, A. Palomo, I. Sobrados, J. Sanz, The role played by the re-
active alumina content in the alkaline activation of fly ashes, Microporous
Mesoporous Mater. 91 (2006) 111–119, https://doi.org/10.1016/j.micromeso.
2005.11.015.
[19] C. Shi, Strength, pore structure and permeability of alkali-activated slag mortars,
Cem. Concr. Res. 26 (1996) 1789–1799, https://doi.org/10.1016/S0008-8846(96)
00174-3.
[20] P. Duxson, A. Fernández-Jiménez, L.J. Provis, G.C. Lukey, A. Palomo, J.S.J. van
Deventer, Geopolymer technology: the current state of the art, J. Mater. Sci. 42
(2007) 2917–2933, https://doi.org/10.1007/s10853-006-0637-z.
[21] M. Ariffin, M. Bhutta, M. Hussin, M. Mohd Tahir, N. Aziah, Sulfuric acid resistance
of blended ash geopolymer concrete, Constr. Build. Mater. 43 (2013) 80–86,
https://doi.org/10.1016/j.conbuildmat.2013.01.018.
[22] F. Puertas, R. Gutierrez, A. Fernández-Jiménez, S. Delvasto, J. Maldonado, Alkaline
cement mortars. Chemical resistance to sulphate and seawater attack, Mater.
Constr. 52 (2002) 55–71, https://doi.org/10.3989/mc.2002.v52.i267.326.
[23] A. Fernández-Jiménez, I. Garcia-Lodeiro, A. Palomo, Durability of alkali-activated
fly ash cementitious materials, J. Mater. Sci. 42 (2007) 3055–3065, https://doi.org/
10.1007/s10853-006-0584-8.
[24] T. Bakharev, J. Sanjayan, Y. Cheng, Resistance of alkali-activated slag concrete to
acid attack, Cem. Concr. Res. 33 (2003) 1607–1611, https://doi.org/10.1016/
S0008-8846(03)00125-X.
[25] O. Burciaga-Díaz, J.I. Escalante-García, Strength and durability in acid media of
alkali silicate-activated metakaolin geopolymers, J. Am. Ceram. Soc. 95 (7) (2012)
2307–2313, https://doi.org/10.1111/j.1551-2916.2012.05249.x.
[26] C. Shi, Corrosion resistance of alkali-activated slag cement, Adv. Cem. Res. 15
(2003) 77–81, https://doi.org/10.1680/adcr.2003.15.2.77.
[27] T. Sugama, L.E. Brothers, T.R. Van de Putte, Acid-resistant cements for geothermal
wells: sodium silicate activated slag/fly ash blends, Adv. Cem. Res. 17 (2005)
65–75, https://doi.org/10.1680/adcr.2005.17.2.65.
[28] J.I. Escalante-García, L. Gómez, K. Johal, G. Mendoza, H. Mancha, J. Méndez,
Reactivity of blast-furnace slag in Portland cement blends hydrated under different
D.E. Ortega-Zavala, et al.
conditions, Cem. Concr. Res. 31 (2001) 1403–1409, https://doi.org/10.1016/
S0008-8846(01)00587-7.
[29] C. Shi, P.V. Krivenko, D. Roy, Alkaline Activators, Alkali-Activated Cements and
Concretes, Taylor and Francis, London, 2006, pp. 6–29.
[30] A.J. Moseson, D.E. Moseson, M.W. Barsoum, High volume limestone alkali-acti-
vated cement developed by design of experiment, Cem. Concr. Compos. 34 (2012)
328–336, https://doi.org/10.1016/j.cemconcomp.2011.11.004.
[31] P. Hawkins, P. Tennis, R. Detwiler, The Use of Limestone in Portland Cement: A
State-of-the-art Review, Portland Cement Association, Illinois, 2003http://
worldcat.org/isbn/0893121487 , Accessed date: 11 March 2019.
[32] EN 197-1, Cement - part 1: composition, specifications and conformity criteria for
common cements, European Committee for Standardization, Brussels, http://www.
rucem.ru/yabbfiles/Attachments/EN-197-1.pdf, (2000) , Accessed date: 11 March
2019.
[33] Cembureau, The European Cement Association, Cement Standards of the World,
Brussels, Belgium, http://www.cembureau.be, (1991) , Accessed date: 11 March
2019.
[34] S. Pandey, R. Sharma, Mineral additions to Portland cement, Chapter 6 in Advances
in Cement Technology: Chemistry, Manufacture and Testing, Tech Books
International, New Delhi, India, 2002.
[35] W. Xiao-Yong, Analysis of hydration and strength optimization of cement-fly ash-
limestone ternary blended concrete, Constr. Build. Mater. 166 (2018) 130–140,
https://doi.org/10.1016/j.conbuildmat.2018.01.058.
[36] U. Avila-López, J.M. Almanza-Robles, J.I. Escalante-García, Investigation of novel
waste glass and limestone binders using statistical methods, Constr. Build. Mater.
82 (2015) 296–303, https://doi.org/10.1016/j.conbuildmat.2015.02.085.
[37] T. Proske, M. Rezvani, S. Palm, C. Müller, C. Graubner, Concretes made of efficient
multi-composite cements with slag and limestone, Cem. Concr. Compos. 89 (2018)
107–119, https://doi.org/10.1016/j.cemconcomp.2018.02.012.
[38] C. Yip, J.L. Provis, G. Lukey, J.S.J. van Deventer, Carbonate mineral addition to
metakaolin-based geopolymers, Cem. Concr. Compos. 30 (2018) 979–985, https://
doi.org/10.1016/j.cemconcomp.2008.07.004.
[39] X. Gao, Q.L. Yu, H.J.H. Brouwers, Properties of alkali activated slag–fly ash blends
with limestone addition, Cem. Concr. Compos. 59 (2015) 119–128, https://doi.org/
10.1016/j.cemconcomp.2015.01.007.
[40] A. Cwirzen, An alkali activated limestone concrete composition and use of com-
position in concrete casting, Europen Patent Office EP 2 514 727 A2, 2012.
[41] J. William, J. McNulty, Inorganic Cemntitious Material, United States US 6,264,740
B1, (2001).
[42] Q. Yin, Z.Y. Wen, Reaction Between Carbonaceous Rocks and Water Glass in 12th
International Congress on the Chemistry of Cement. Montreal Canada, (2007), p. 5.
[43] ASTM C204-07 Standard Test Methods for Fineness of Hydraulic Cement by Air-
Permeability Apparatus, ASTM International, West Conshohocken, PA (19428-
2959).
[44] ACI 211-1, Standard Practice for Selecting Proportions for Normal, Heavyweight
and Mass Concrete, vol. 211, ACI Committee, 2009 (Reapproved).
[45] http://crmht-europe.cnrs-orleans.fr/dmfit/ , Accessed date: 11 March 2019.
[46] C. Yip, J.S.J. van Deventer, Microanalysis of calcium silicate hydrate gel formed
within a geopolymeric binder, J. Mater. Sci. 38 (2003) 3851–3860, https://doi.org/
10.1023/A:1025904905176.
[47] O. Burciaga-Díaz, R.X. Magallanes-Rivera, J.I. Escalante-García, Alkali-activated
slag-metakaolin pastes: strength, structural, and microstructural characterization, J.
Sustainable Cem. Mater. 2 (2013) 111–127, https://doi.org/10.1080/21650373.
2013.801799.
[48] O. Burciaga-Díaz, J.I. Escalante-García, Structure, mechanisms of reaction, and
strength of an alkali-activated blast-furnace slag, J. Am. Ceram. Soc. 96 (12) (2013)
3939–3948, https://doi.org/10.1111/jace.12620.
[49] R. Arellano-Aguilar, O. Burciaga-Díaz, A. Gorokhovsky, J.I. Escalante-García,
Geopolymer mortars based on a low grade metakaolin: effects of the chemical
composition, temperature and aggregate:binder ratio, Constr. Build. Mater. 50
(2014) 642–648, https://doi.org/10.1016/j.conbuildmat.2013.10.023.
[50] N.R. Rakhimova, R.Z. Rakhimov, N.I. Naumkina, A.F. Khuzin, Y.N. Osin, Influence
of limestone content, fineness, and composition on the properties and micro-
structure of alkali-activated slag cement, Cem. Concr. Compos. 72 (2016) 268–274,
https://doi.org/10.1016/j.cemconcomp.2016.06.015.
[51] J.I. Escalante-García, A.F. Fernandez, A. Gorokhovsky, P.L. Fraire, G. Mendoza-
Suarez, Hydration products and reactivity of blast furnace slag activated by various
alkalis, J. Am. Ceram. Soc. 86 (2003) 2148–2153, https://doi.org/10.1111/j.1151-
2916.2003.tb03623.x.
[52] M. Mette, H. Duncan, S. Mette, F.K. Lise, Y. Yuanzheng, Physical performances of
blended cements containing calcium aluminosilicate glass powder and limestone,
Cem. Concr. Res. 41 (2011) 359–364, https://doi.org/10.1016/j.cemconres.2010.
12.005.
[53] S. Bernal, J.L. Provis, V. Rose, R. Mejía de Gutiérrez, Evolution of binder structure
in sodium silicate-activated slag-metakaolin blends, Cem. Concr. Compos. 33
(2011) 46–54, https://doi.org/10.1016/j.cemconcomp.2010.09.004.
[54] Y. Ping, R. James, P. Brent, P.F. McMillan, C. Xiandong, Structure of calcium silicate
hydrate (C-S-H): near-, mid-, and far-infrared spectroscopy, J. Am. Ceram. Soc. 82
(1999) 742–748, https://doi.org/10.1111/j.1151-2916.1999.tb01826.x.
[55] I. García-Lodeiro, Compatibilidad de geles cementantes csh y nash. Estudios en
278
Cement and Concrete Research 120 (2019) 267–278
muestras reales y en polvos sintéticos (Tesis doctoral), Universidad Autónoma de
Madrid, Departamento de Química Inorgánica, 2008, http://hdl.handle.net/10486/
1340 , Accessed date: 11 March 2019.
[56] F. Puertas, M. Palacios, H. Manzano, J.S. Dolado, A. Rico, J. Rodríguez, A model for
the C-A-S-H gel formed in the alkali-activated slag cements, J. Eur. Ceram. Soc. 31
(2011) 2043–2056, https://doi.org/10.1016/j.jeurceramsoc.2011.04.036.
[57] F. Puertas, S. Martínez-Ramírez, S. Alonso, T. Vázquez, Alkali-activated fly ash/slag
cements: strength behavior and hydration products, Cem. Concr. Res. 30 (2000)
1625–1632, https://doi.org/10.1016/S0008-8846(00)00298-2.
[58] I. García-Lodeiro, A. Fernández-Jiménez, A. Palomo, D.E. Macphee, Effect on fresh
C-S-H gels of the simultaneous addition of alkali and aluminum, Cem. Concr. Res.
40 (2010) 27–32, https://doi.org/10.1016/j.cemconres.2009.08.004.
[59] C.K. Yip, G.C. Lukey, J.L. Provis, J.S.J. van Deventer, Carbonate mineral addition to
metakaolin based geopolymers, Cem. Concr. Compos. 30 (2008) 979–985, https://
doi.org/10.1016/j.cemconcomp.2008.07.004.
[60] V. Teresa, M. Piqué, Uso de Espectroscopía Infrarroja con Transformada de Fourier
(FT IR) en el estudio de la hidratación del cemento. Concreto y Cemento, Investig.
Desarro. 3 (2012) 62–71 http://www.redalyc.org/articulo.oa?id=361233550004 ,
Accessed date: 11 March 2019.
[61] I. García-Lodeiro, D.E. Macphee, A. Palomo, A. Fernández-Jiménez, Effect of alkalis
on fresh C–S–H gels. FTIR analysis, Cem. Concr. Res. 39 (2009) 147–153, https://
doi.org/10.1016/j.cemconres.2009.01.003.
[62] I. García-Lodeiro, A. Fernández-Jiménez, M. Teresa Blanco, A. Palomo, FTIR study
of the sol–gel synthesis of cementitious gels: C-S-H and N-A-S-H, J. Sol-Gel Sci.
Technol. 45 (2008) 63–72, https://doi.org/10.1007/s10971-007-1643-6.
[63] M. Criado, A. Palomo, A. Fernández-Jiménez, Alkali activation of fly ashes part I:
effect of curing conditions on the carbonate of the reaction products, Fuel 84 (2005)
2048–2054, https://doi.org/10.1016/j.fuel.2005.03.030.
[64] S. Caijun, A. Fernández Jiménez, A. Palomo, New cements for the 21st century: the
pursuit of an alternative to Portland cement, Cem. Concr. Res. 41 (2011) 750–763,
https://doi.org/10.1016/j.cemconres.2011.03.016.
[65] Z.H. Zhang, H. Wang, J.L. Provis, F. Bullen, A. Reid, Y.C. Zhu, Quantitative kinetic
and structural analysis of geopolymers. Part 1. The activation of metakaolin with
sodium hydroxide, Thermochim. Acta 539 (2012) 23–33, https://doi.org/10.1016/
j.tca.2012.03.021.
[66] A. Fernández-Jiménez, Cementos de escorias activadas alcalinamente: influencia de
las variables y modelización del proceso (Tesis doctoral), Universidad Autónoma de
Madrid. Departamento de Química Inorgánica, 2000, http://hdl.handle.net/10486/
13323 , Accessed date: 11 March 2019.
[67] K. Mackenzie, M. Smith, Multinuclear Solid-state NMR of Inorganic Materials,
Pergamon, Amsterdam, Boston, London, New York, Oxford, Paris, San Diego, San
Francisco, Singapore, Sydney, Tokyo, 2002, pp. 63–77.
[68] G. Engelhardt, Multinuclear solid-state NMR in silicate and zeolite chemistry, TrAC
Trends Anal. Chem. 8 (9) (1989) 343–347, https://doi.org/10.1016/0165-
9936(89)87043-8.
[69] F. Puertas, M. Hérnandez, C. Varga, S. Goñis, A. Guerrero, Proceso de deterioro por
descalcificación del cemento: estudio comparativo de elementos de diferente
composición, Consejo Superior de Investigaciones Científicas, Madrid, 2013.
[70] H. Stade, On the reaction of C-S-H (di. Poly) with alkali hydroxides, Cem. Concr.
Res. 19 (1989) 802–810, https://doi.org/10.1016/0008-8846(89)90051-3.
[71] D.E. Macphee, K. Luke, F. Glasser, E. Lachowski, Solubility and aging of calcium
silicate hydrates in alkaline solutions at 25°C, J. Am. Ceram. Soc. 72 (1989)
646–654, https://doi.org/10.1111/j.1151-2916.1989.tb06189.x.
[72] H. Viallis, P. Faucon, J.-C. Petit, A. Nonat, Interaction between salts (NaCl, CsCl)
and calcium silicate hydrates (C–S–H), J. Phys. Chem. B 103 (1999) 5212–5219,
https://doi.org/10.1021/jp983757+.
[73] S. Sarkar, X. Aimin, D. Jana, Scanning electron microscopy, X-ray microanalysis of
concretes, Handbook of Analytical Techniques in Concrete Science and
Technologies, Noyes Publications, 2001, pp. 231–274 (Cap. 7).
[74] S.Y. Hong, F.P. Glasser, Alkali sorption by C-S-H and C-A-S-H gels part II. Role of
alumina, Cem. Concr. Res. 32 (2002) 1101–1111, https://doi.org/10.1016/S0008-
8846(02)00753-6.
[75] H.F.W. Taylor, A method for predicting alkali ion concentrations in cement pore
solutions, Adv. Cem. Res. 1 (1) (1987) 5–16, https://doi.org/10.1680/adcr.1987.1.
1.5.
[76] E. Gartner, Industrially interesting approaches to “low-CO2” cements, Cem. Concr.
Res. 34 (9) (2004) 1489–1498, https://doi.org/10.1016/j.cemconres.2004.01.021.
[77] L. Turner, F. Collins, Carbon dioxide equivalent (CO2-e) emissions: a comparison
between geopolymer and OPC cement concrete, Constr. Build. Mater. 43 (2013)
125–130, https://doi.org/10.1016/j.conbuildmat.2013.01.023.
[78] B. McLellan, R. Williams, J. Lay, A. van Riessen, G. Corder, Costs and carbon
emissions for geopolymer pastes in comparison to ordinary Portland cement, J.
Clean. Prod. 19 (2011) 1080–1090, https://doi.org/10.1016/j.jclepro.2011.02.010.
[79] M. Fawer, M. Concannon, W. Rieber, Life cycle inventories for the production of
sodium silicates, Int. J. LCA 4 (4) (1999) 207–212, https://doi.org/10.1007/
BF02979498.
[80] F. Pacheco-Torgal, J. Labrincha, C. Leonelli, A. Palomo, P. Chindaprasit, Life cycle
assessment (LCA) of alkali-activated cements and concretes, Handbook of Alkali-
activated Cements, Mortars and Concretes, Woodhead Publishing, 2014, p. 671
(Cap 25).