Construction and Building Materials 189 (2018) 109–118

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Construction and Building Materials

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Review

Natural volcanic pozzolans as an available raw material

for alkali-activated materials in the foreseeable future: A review
Rafael Andres Robayo-Salazar, Ruby Mejía de Gutiérrez ⇑
Composites Materials Group (CENM), Universidad del Valle, Cali, Colombia

h i g h l i g h t s

 The paper reviews the utilization of natural volcanic pozzolan (NPs) in the production of AAM.
 The available raw materials are a vital aspect for the technological transition of the AAM.
 This review analyzed the role of characteristics of NPs in the alkaline activation.
 This paper can encourage and promote the research on the alkaline activation of NPs.
 This review presents the future challenges and opportunities in this topic.

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

Article history: Alkali-activated materials (AAM) represent a line of research of great interest around the world as a real
Received 28 June 2018 alternative to replace Portland cement (OPC). Despite this global interest, it is believed that current and
Received in revised form 19 August 2018 future research should focus on overcoming the challenges that this technology faces with regard to its
Accepted 27 August 2018
application at an industrial level. One of the main barriers to scale at the industrial level is the scarcity of
studies on truly available and sustainable raw materials (precursors and activators). This review empha-
sizes natural volcanic pozzolans (NPs), also named volcanic ashes, as a globally available and sustainable
Keywords:
raw material for industrial production of AAM in the foreseeable future. To this end, the most important
Alkali-activated materials
Natural volcanic pozzolans
findings about mechanical performance and durability reported by researchers at a global level are pre-
Volcanic ashes sented and described, and a constructive analysis is carried out in order to establish the future challenges
Mechanical performance and opportunities to carry out a technological transition of these advances (industrial application) in
Durability countries rich in materials derived from volcanic activity.
Ó 2018 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
2. Roles of characteristics and properties of natural volcanic pozzolans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2.1. Chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2.2. Mineralogical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2.3. Reactivity and pre-treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
3. Alkaline activation of natural volcanic pozzolans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
3.1. The effect of type-concentration of the alkaline activator and curing conditions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
3.2. Importance of calcium/aluminium incorporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4. Durability of natural volcanic pozzolan-based alkali activated materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
6. Future challenges and opportunities. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116

⇑ Corresponding author.
E-mail address: ruby.mejia@correounivalle.edu.co (R. Mejía de Gutiérrez).

https://doi.org/10.1016/j.conbuildmat.2018.08.174
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
110 R.A. Robayo-Salazar, R. Mejía de Gutiérrez / Construction and Building Materials 189 (2018) 109–118

7. Final comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116

Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

1. Introduction PAS 8820: 2016 ‘‘Construction materials. Alkali-activated cementi-

tious material and concrete. Specification” emerges as the UK’s strat-
In the search for new cementitious materials that have a global egy for encouraging the use of these materials in the construction
warming potential (GWP) lower than that of ordinary Portland industry and for achieving some of the proposed objectives for this
cement (OPC)—that is to say, whose manufacturing processes are sector by 2025.
less energy intensive—there have been, among others, (1) so- The SCMs commonly used to produce GP, AACs and/or HYCs are
called ‘‘blended cements,” which involve the partial replacement metakaolin (MK), fly ashes (FA) and granulated blast furnace slags
of clinker by supplementary cementitious materials (SCMs), such (GBFS), with extensive and satisfactory studies reported since the
as natural pozzolans or industrial by-products; (2) ‘‘alkali- last century by various authors worldwide [9–13]. Despite the
activated cements and concretes” (AACs), including so-called excellent properties reported for FA- or GBFS-based AACs, the very
‘‘geopolymers” (GPs), which allow the use of SCMs (100%) as the nature of these precursors which are by-products from CO2
base material, giving rise to OPC-free cements; and (3) ‘‘hybrid producing industries means their chemical and mineralogical com-
cements” (HYCs), also known as ‘‘alkali-activated Portland blended position are variable, making it difficult to standardize an alkaline
cement”, [1] which combine the two technologies, i.e., the positive activation process for its introduction to the market [14]. In
effects of OPC with AACs. This search implies the production of bin- addition, the global production of these by-products is limited—
ders based on a high content of SCMs (70%) and a low level of OPC 500–700 Mt/year for FA [15] and 170–250 Mt/year for GBFS
addition (30%) [1–3]. The production of AACs eliminates the pro- [16]—compared to global production of OPC (3–4 trillion tons/
cess of clinkerization, which leads to a significant reduction of CO2 year) [17]. Such proportions limit the replacement of OPC with a
emissions linked to the process necessary in the manufacture of cement system based exclusively (100%) on the alkaline activation
OPC [4]; it is estimated that this reduction would reach values of these materials. The global demand for OPC by 2030 is projected
close to 70%, which is relevant considering that, today, the cement to increase by 216%; in this same period, the generation of FA and
industry is responsible for 5–7% of the CO2 emitted into the atmo- GBFS may increase by only 15% [18]. Provis [19] added that, at
sphere, and it is estimated that this figure will exceed 10–15% by present, the use of quality FA or GBFS precursors can achieve a
2020 [5–8]. price similar to the unit price of OPC, and mentioned that the use
Standards, such as ASTM C1157-11 ‘‘Standard Performance Spec- of aluminosilicates, also used by the cement industry in the
ification for Hydraulic Cement” in the USA and, recently, NTC 121 production of ‘‘blended cements”, makes this industry its main
(third update) ‘‘Performance Specification for Hydraulic Cement” in competitor. In this sense, it is reasonable to think now about the
Colombia, classified cements based their performance rather than use of FA and GBFS as correctors or modifiers in the production
composition, which allows the introduction to the market of these of alkali-activated binary cements, where the by-product content
new types of binders that are more environmentally friendly and is low (30%) and whose precursor base (70%) is a material of
feature mechanical properties and durability equal to or greater greater availability and homogeneity.
than conventional options using OPC. In recent years, RILEM and The local availability of natural volcanic pozzolans (NPs) in sig-
ASTM committees have been formed for the study and/or stan- nificant quantities is promoted as a viable alternative (from the
dardization of these cement products (AACs), seeking the formula- commercial point of view) for the adoption of AACs on an indus-
tion of standards and recommendations for their implementation trial scale because there would be better quality control of raw
in different civil infrastructure applications. In effect, the standard materials [20–23]. NPs deposits account for approximately 0.84%

Fig. 1. Global distribution of NPs deposits (grey areas). Source: [28].

 R.A. Robayo-Salazar, R. Mejía de Gutiérrez / Construction and Building Materials 189 (2018) 109–118 111

process (or geopolymerization) of NPs, when is used as precursor,

and the mechanical performance and durability of these materials,
and ends with a general discussion of the challenges and opportu-
nities for a technological transition towards its use. It is considered
that NPs may in the foreseeable future, provide a sustainable and
technically feasible raw material for the production of AACs on
an industrial scale approximating that of the current production
of OPC in countries rich in soils derived from volcanic activity.

2. Roles of characteristics and properties of natural volcanic

pozzolans

Volcanic ash generated by magma fragmentation gives rise to

Fig. 2. Papers published in the last 18 years (2000- to June 2018) in the field of
alkali-activation of natural volcanic pozzolans (NPs) vs. geopolymers and alkali-
activated materials (Source: Scopus). Search of keywords in: article title, abstract
and keywords.
of the world’s soils (124 million hectares), distributed predomi-
nantly, although not exclusively in tropical regions [24] (see
Fig. 1). Soils derived from volcanic ash are common in countries
such as Iran, Cameroon, Japan, China, Saudi Arabia, Turkey, Jordan,
Italy, Greece, USA, Mexico, Chile, Ecuador and Colombia [25],
among others, where deposits of NPs are usually concentrated in
areas of high demographic and economic growth. For example, in
Colombia, NPs constitute 11% of the territory and are concentrated
in the central and southwestern areas; in Chile, they account for
50% of the country’s total arable land, concentrated significantly
among metropolitan regions; and in Japan, they account for 18%
of the territory [26,27]. It also bears mention that southern Europe
is the original source of pozzolans.
A careful review of the scientific literature showed that the
number of publications on alkaline activation of NPs does not sur-
pass 60 articles (Keywords: alkali-activated/geopolymer natural
volcanic pozzolan), in contrast to the more than 7000 articles pub-
lished over the last 18 years (2000–2018) on alkali-activated mate-
rials and geopolymers (see Fig. 2; searches in Scopus). Notably,
despite there being few publications, the results obtained are gen-
erally satisfactory and demonstrate the potential of NPs as possible
primary precursors for AACs. This review describes, based on these
scientific reports, the factors that influence the alkaline activation
NPs through physical and chemical alteration processes (i.e., disso-
lution, leaching and precipitation of compounds). The mechanism
behind the formation of volcanic ash, environmental conditions
during the weathering process and time play important roles with
regard to the final properties and characteristics of NPs [24,27,29].
This review presents the main characteristics and/or properties of
NPs that influence their alkaline activation or geopolymerization.
2.1. Chemical composition
During the weathering of NPs, an elemental composition rich in
Si, Al, Fe, Ca, Mg, K and Na base cations is usually obtained. The
content of silica usually predominates, based on this value and
the Na2O + K2O content, they are classified as; rhyolitic (>77%
SiO2), dacitic (63–77% SiO2), andesitic (57–63% SiO2), basalt-
andesitic (52–57% SiO2) and basaltic (45–52% SiO2) [30,31]. The
loss on ignition (LOI) is generally low but may reach values greater
than 10% by weight when NPs contain some zeolite or clay-type
minerals. Table 1 presents the classification and chemical compo-
sition of some NPs used by various authors in the field of alkaline
activation at a global level.
2.2. Mineralogical composition
Most NPs are rich in minerals such as feldspars (anorthite
(CaAl2Si2O8)-albite (NaAlSi3O8) series) belonging to the group of
plagioclases; amphiboles (hornblende and tremolite minerals);
micas (biotite and muscovite minerals); pyroxenes and a minority
quartzes and clays [43–48] (Table 2). In general, the mineralogical
composition (crystalline phase) of NPs can be understood by relat-
ing their chemical composition and the interaction of these ele-
ments during the weathering process, which occurs under the
influence of variables such as temperature, pressure and time (nat-
ural catalysts of the reactions). According to Palomo et al. [49] and

Table 1
Chemical composition (% by weight of oxides) of some NPs used in the alkaline activation field.

Country Type SiO2 Al2O3 Fe2O3 CaO Na2O MgO K2O LOI Ref.
Iran Taftan Andesite 61.57 18.00 4.93 6.69 1.65 2.63 1.95 2.15 [32]
Shahindej Dacite 70.13 11.11 1.27 2.52 1.01 0.92 2.25 10.28 [33]
Sahand Dacite 64.67 11.85 3.03 6.79 2.3 1.11 4.26 5.15
Sirjan Dacite 68.51 11.84 3.73 2.90 1.62 1.43 3.19 6.14
Rafsanjan Andesite 68.31 12.59 2.70 3.88 2.40 1.37 3.26 4.41
Cameroon Foumbot Basaltic 44.19 14.06 13.22 10.38 3.69 9.73 1.53 0.62 [34]
Galim Basaltic 41.36 15.41 12.88 7.88 2.22 6.45 0.90 9.31 [35]
Saudi Arabia Basaltic 46.48 14.74 12.16 8.78 3.39 8.73 1.27 1.32 [36]
Japan Basaltic-Andesite 54.93 16.44 10.89 8.79 2.84 3.30 1.72 [37]
Jordanian Basaltic 40.17 13.86 15.16 9.70 3.66 9.57 1.53 4.75 [38]
Bulgaria Clinoptilotite Dacite 62.74 9.68 0.74 6.73 0.29 2.90 2.79 13.74 [39]
México Basaltic-Andesite 55.73 13.27 3.80 5.41 0.80 2.67 2.15 15.50 [40]
EUA Dacite 68.8 8.5 1.1 3.2 5.2 3.7 [41]
Colombia Andesite 61.99 15.52 7.33 5.19 4.07 2.49 1.59 0.48 [42]
General range 40–70 10–20 1–15 2–10 1–5 1–10 1–5 <10
112 R.A. Robayo-Salazar, R. Mejía de Gutiérrez / Construction and Building Materials 189 (2018) 109–118

Table 2
Overview of the mineralogical composition of NPs.

Mineral group Mineral sub-group Mineral Chemical formula

Feldspar Plagioclase Anorthite CaAl2Si2O8
Albite NaAlSi3O8
Alkali feldspar Microcline KAlSi3O8
Sanidine
Orthoclase
Anorthoclase (Na,K)AlSi3O8
Feldspathoid Nepheline (Na,K)AlSiO4
Amphibole Tremolite Ca2Mg5Si8O22(OH)2
Hornblende (Ca,Na)2–3(Mg,Fe,Al)5Si6(Al,Si)2O22(OH)2
Silica Quartz SiO2
Pyroxene Clinopyroxenes Augite (Ca,Na)(Mg,Fe,Al,Ti)(Si,Al)2O6
Diopside CaMgSi2O6
Orthopyroxenes Enstatite Mg2Si2O6
Clay minerals Montmorillonite (Na,Ca)0.33(Al,Mg)2(Si4O10)(OH)2
nH2O
Halloysite Al2Si2O5(OH)4
Mica Biotite K(Mg,Fe)3(AlSi3O10)(F,OH)2
Muscovite KAl2(AlSi3)O10(OH)2

Krivenko [50], the natural precipitation of these sodium-calcium
feldspars helps in understanding the mechanism of artificial syn-
thesis of AACs via ‘‘alkaline activation” or ‘‘geopolymerization”.
2.3. Reactivity and pre-treatments
The reactivity of the NPs in alkaline medium (pozzolanic activ-
ity) depends mainly on the vitreous phase content (related to the
thermal history of NP), the content of soluble silica and alumina
species (SiO2/Al2O3 molar ratio of vitreous phase) and particle size.
Bondar et al. [33], Tchakoute et al. [51], Takeda et al. [37], Djobo
et al. [52] and Robayo-Salazar et al. [42] reported vitreous phase
contents close to 30%. In this regard, Ndjock et al. [53] showed that
depending on the SiO2/Al2O3 ratio of the vitreous phase, NPs can be
classified as suitable (reactive: SiO2/Al2O3  3.9) or non-suitable
(filler: SiO2/Al2O3 > 3.9) for obtaining ‘‘geopolymers” or AACs. How-
ever, in most cases, the methods for quantifying this via chemical
reaction give rise to confusing results. Bondar et al. [54] demon-
strated how the solubility of some NPs (dacitic and andesitic) could
be increased after being calcined at temperatures below 700 °C
(thermal activation) but in contrast, at 900 °C, solubility decreases.
These types of thermal treatments have also been used to reduce
the content of clay minerals present in some NPs [21], which,
due to their laminar structure, exhibit a high absorption that
affects the synthesis of AACs. Alkaline melt processes (in the pres-
ence of NaOH) at elevated temperatures have resulted in a signifi-
cant increase of reactivity of NPs. Tchakoute et al. [55] reported
vitreous phase contents up to 76% as a result of an fusing in alkali
at 550 °C for 1 h (Al2O3/Na2O molar ratio of 0.13). Djobo et al. [52]
described a considerable increase in the rate and degree of reaction
of a basaltic NP by decreasing its particle size by milling.
3. Alkaline activation of natural volcanic pozzolans
3.1. The effect of type-concentration of the alkaline activator and
curing conditions
In general, the main variables involved in the synthesis of AACs,
regardless of the precursor used, are related to the characteristics
of the alkaline activator (type and concentration) and curing condi-
tions (temperature, time and humidity). Regarding the alkaline
activator, pH, concentration, solubility, type of alkali metal and
its nature (solid or liquid) have been identified as playing impor-
tant roles. Activators commonly used in alkaline activation include

Table 3
Summary of the effect of alkaline activator type and concentration and the curing conditions on the compressive strength of some AACs based (100%) on NPs.

Activator Concentration Curing treatment CS (MPa) Optimal conditions Ref.

Ca(OH)2 5–50% (weigh) 28 days to 50 °C 18.8–38.7 Ca(OH)2 = 20% [56]
NaOH Na2O/SiO2 = 0.15–0.35 5 days to 40–90 °C (wet and dry) up to 55 Na2O/SiO2 = 0.30 [34]
5 days to 90 °C
NaOH Na2O = 4–10% 28 days to 25 °C up to 47 MS = 0.60 [32]
Na2SiO3 MS = 0.52–0.68 Na2O = 10%
NaOH Na2O/Al2O3 = 0.92–1.23 5–20 h to 25–85 °C up to 57.5 Na2O/Al2O3 = 1.2 [57]
Na2SiO3 SiO2/Al2O3 = 5.98–6.00 SiO2/Al2O3 = 5.9
20 h to 85 °C
KOH/NaOH NaOH/KOH = 2–10 M 27 days to 40/60 °C up to 56.2 NaOH/KOH = 5–7.5 M [58]
Na2SiO3 MS = 2.1–3.1 MS = 2.1
27 day to 60 °C
NaOH Na2O/Al2O3 = 0.61–1.23 28 days to 25 °C up to 45 (25 °C) Na2O/Al2O3 = 0.92 [59]
Na2SiO3 MS = 0.30–0.90 45–125 °C for 20 h MS = 0.75
NaOH MS = 0.70–1.40 28 days to 25 °C 23–50 MS = 1.4 [60]
Na2SiO3
NaOH NaOH = 10 M 1, 3, 7, y 28 days up to 47 28 days to 80 °C [36]
Na2SiO3 80%NaOH + 20%Na2SiO3 80 °C (100% RH)
NaOH NaOH = 8–12 M 24 h to 27–80 °C up to 28 24 h to 80 °C [61]
Na2SiO3 MS = 1.40–1.66 MS = 1.4
NaOH Na2O/Al2O3 = 0.06–0.15 48 h to 70 °C up to 64 MPa Na2O/Al2O3  0.09 [62]
Na2SiO3 SiO2/Al2O3 = 6.5–8.0 SiO2/Al2O3 = 7.3–7.5

MS = silica modulus; CS = compressive strength; ST = setting time; HR = heat of reaction; RH = relative humidity.
 R.A. Robayo-Salazar, R. Mejía de Gutiérrez / Construction and Building Materials 189 (2018) 109–118
hydroxides (ROH, R(OH)2), weak acid salts (R2CO3), strong acid
salts (Na2SO4, CaSO4
2H2O), and silica salts (R2O(n)SiO2), where R
is an alkali metal ion, Na, K or Li. In general, an increase in the con-
centration of alkaline activator allows a greater dissolution of the
precursor. However, there is a limit beyond which the properties
of the AACs can be affected. Of course, variables related to the cur-
ing treatment such as temperature, curing time and relative
humidity also have an effect on the kinetics of the reactions. Table 3
summarizes the effect of alkaline activator type and concentration
and the curing conditions on the compressive strength of different
alkaline-activated NPs.
Kani and Allahverdi [57] used NaOH + Na2SiO3 as the alkaline
solution (activator) and evaluated different temperatures (45, 65
and 85 °C) and times (5, 10, 15 and 20 h) of hydro-thermal curing,
after 1 and 7 days of pre-curing. The results obtained demon-
strated that a longer curing time and higher temperature yielded
the best mechanical performance, with 85 °C for 20 h (after 7 days
of pre-curing) being the optimal condition (57 MPa). The authors
stated that a humid atmosphere (95%) was a key variable for
strength development of a mixture cured at 25 °C for 28 days, this
combination yielded a compressive strength of up to 37.5 MPa.
Under the same conditions (25 °C and 95% relative humidity),
Allahverdi et al. [32] achieved up to 47 MPa at 28 days. In contrast,
Tarxiachou et al. [63] reported the need to apply 70 °C for 5 days to
reach strength levels on the order of 34 MPa at 28 days, also using
NaOH + Na2SiO3 as the alkaline activator.
Autoclave-curing processes (pressures and elevated tempera-
tures) have also been applied to accelerate reactions. Kani and
Allahverdi [57] reported compressive strengths of up to 108 MPa
at 7 days after autoclaving at 210 °C for 30 h; this represents an
increase of 88% of the strength at 85 °C for 20 h (Table 3). In con-
trast, Bondar et al. [58] reported similar strengths (40–45 MPa)
when comparing samples cured at 60 °C for 27 days and cured in
an autoclave (2.5 MPa of pressure) at 150 °C for 3 h.
Kani et al. [59] reported that increasing the Na2O/Al2O3 molar
ratio not only promoted the generation of higher strengths but also
a higher leaching of free alkalis as an indicator of efflorescence.
They also reported how this leaching could be controlled with
the application of a post-curing hydro-thermal treatment at tem-
peratures between 45 and 125 °C. Kani and Allahverdi [64]
reported that increasing the SiO2/Al2O3 and Na2O/Al2O3 molar
ratios promotes greater shrinkages (length changes), which,
although they may also be counteracted by hydrothermal curing
processes, could compromise their use in some applications. In this
regard, Bondar et al. [65] claimed that in addition to the curing pro-
cess (temperature and humidity), the water/binder ratio was the
main variable that affected the shrinkage of NP-based AACs. How-
ever, this length change was smaller than for OPC. Tchakoute et al.
[60] reported how increasing the solution modulus (Ms: SiO2/
Na2O) of the activator promotes greater strength but at the same
time affects the setting time of binder. Djobo et al. [61] reported
similar results and finds that increasing the Ms, promotes a greater
heat of reaction, especially during the first period associated with
NP dissolution.
Bondar et al. [58] used granular, powdered and solution (water-
glass) Na2SiO3 as activators finding that among the three types of
silicate, waterglass yields the best performance (43 MPa). In addi-
tion, they reported that KOH generated greater strength than
NaOH, more so when a thermal curing is applied, obtaining com-
pressive strengths of 32.2 and 56.2 MPa, respectively, after 27 days
of curing at 40 and 60 °C. Finally, they added that the optimum
solution modulus (Ms) of the activator depended on the CaO con-
tent present in the NP. Nadoushan and Ramezanianpour [66], after
an extensive evaluation of variables such as molarity (6–10 M), Ms
(2.10–3.13) and type of activator (NaOH/KOH and Na2SiO3) in the
mixture, concluded that the use of KOH is mechanically more
113
efficient than NaOH; their explanation is based on the larger size
of the K+ ions relative to Na+, hence the formation of a more com-
pact and stronger structure. In contrast to these results, Lemougna
et al. [67] found that NaOH promotes a faster reaction rate and
greater ultimate compressive strength than KOH. On the other
hand, Robayo-Salazar et al. [62] reported that the addition of Na2-
SiO3 (soluble Si-O species) resulted in an increase in the compres-
sive strength of 165% with respect to the mixture activated with
NaOH (24 MPa) and highlighted the need to apply a thermal curing
at 70 °C for 48 h to achieve strengths up to 64 MPa. Similarly, Moon
et al. [36] reported that the addition of Na2SiO3 (20% by weight rel-
ative to NaOH) increases the strength at 28 days of curing (80 °C) of
the NaOH-activated mixtures by 42%. Ortega et al. [56] reported
compressive strengths up to 38.7 MPa at 28 days of curing at
50 °C using reagent-grade Ca(OH)2 as an alkaline activator.
Up until now, results with solids activators such as Na2CO3 or
Na2SO4 have not been reported for the case of NPs; it is worth not-
ing that these activators are of industrial interest because of their
low cost, availability and negligible levels of CO2 emissions (global
warming potential; GWP) compared to common activators
(hydroxides and silicates). Alternative activators to sodium silicate
produced from industrial wastes (rice husk ash, waste glass, silica
fume and spent diatomaceous earth) mixed with NaOH also have
not been evaluated in the alkaline activation of NPs; it should be
noted that with the use of other common precursors, interesting
results have been reported [68–71].
These results demonstrate that the adjustment of variables such
as the type and concentration of the alkaline activator and the opti-
mum curing conditions depend on the type and reactivity of each
NP. The curing conditions (temperature, curing time and humidity)
also have a significant influence on the performance of NP-based
AACs, especially those with low reactivity. On the other hand, the
addition of Na2SiO3 (a soluble Si-O species) to solutions of NaOH
is the best option as an alkaline activator. Nevertheless, as
mentioned above, there is a need to study the use of alternative
activators (solid type) and those produced from industrial wastes
or by-products.
3.2. Importance of calcium/aluminium incorporation
Fig. 3 plots in a CaO-SiO2-Al2O3 ternary diagram, the chemical
composition of the volcanic rocks or NPs and some SCMs or precur-
sors commonly used in alkaline activation technology (MK, FA and
GBFS) [28]. NPs have high SiO2 content and are deficient in Al2O3 in
Fig. 3. Ternary CaO-SiO2-Al2O3 diagram (wt % based) situating the chemical
constitution of NPs (volcanic rocks) vs. the common SCMs. Source: [28].
114 R.A. Robayo-Salazar, R. Mejía de Gutiérrez / Construction and Building Materials 189 (2018) 109–118

Table 4
Summary of the effect of the addition of supplementary sources of reactive Al2O3 and calcium on the compressive strength of some AACs based on NPs.

Activator Mineral Addition (MA) Optimal MA (% in weigh) CS (MPa) (28 days) Ref.
100%NP Binary (25 °C)
NaOH MK 40 36.1 47.8 [35]
Na2SiO3
NaOH MK 25 N.R. 68.8 [78]
Na2SiO3
NaOH MK 20 N.R. (NP1) 68.7 (NP1) [42]
Na2SiO3 13.0 (NP2) 43.0 (NP2)
NaOH CAC 6 32.5 70.0 [59]
Na2SiO3 MK 8 45.0
NaOH CAC 24 18.0 65.0 [76]
Na2SiO3
NaOH GBFS 5 36.0 36.0 [74]
Na2SiO3
NaOH GBFS 30 13.0 48.1 [21]
Na2SiO3
NaOH GBFS 30 N.R. 125.0 [62]
Na2SiO3
KOH GBFS 5 127.4 147.1 [66]
Na2SiO3

CS = compressive strength; GBFS = Granulated Blast Furnace Slag; MK = Metakaolin; CAC = Calcium Aluminate Cement; BL = burnt lime; N.R. = not reported.

relation to the common precursors and, also, of CaO in relation to
the GBFS and some classes of FA. As for the content of SiO2 and
Al2O3, it should be clarified that is the reactive fraction, which
undoubtedly makes a difference for each of these precursors, pos-
itively or negatively affecting its performance during alkaline acti-
vation [72,73]. In this sense, it is worth mentioning that, depending
on the efficient thermal control carried out during the processes of
obtaining the MK and sub-products such as FA and GBFS, high vit-
reous fractions are achieved. Although the NPs also have a thermal
history, the cooling process depends on variables controlled by
nature rather than by humans (i.e., temperature, pressure, wind
speed and humidity, among others); as a result, most NPs do not
reach vitreous fractions similar to MK, FA or GBFS, and their values
normally are between 30 and 70% [33,37,42,51,52].
Consequently, supplementary sources of calcium, such as GBFS
[21,59,62,66,74], ‘‘burnt lime” (BL) [75] and ‘‘calcium aluminate
cement” (CAC) [59,76,77], and reactive Al2O3, such as MK
[35,42,51,55,59,78], have been successfully evaluated as composi-
tional correctors of NPs to obtain AACs (Table 4). Like the reactive
phase of NPs, these additions interact in the alkaline environment
with OH– and promote the breaking of its reactive structure, gen-
erating based on their chemical compositions dissolved species of
Ca2+, [H2SiO4]2 , [H3SiO4] and [HAlO4] , which can precipitate
and generate nucleation and, depending on their concentration,
N-A-S-H and/or C-S-H type reaction products, which have been
shown to react over time and, as a result of this interaction, form
(N,C)-A-S-H and/or C-A-S-H type gels [79–83].
Tchakoute et al. [35] reported an increase in the compressive
strength of 18.1 and 32.4% with the addition of 20 and 40% of
metakaolin to NPs, respectively; this behaviour is attributed to
the increase of intermediate species of [SiO (OH)3] and [Al
(OH)4] in the system and its participation in the formation of N-
A-S-H-type gels. Djobo et al. [78] reported compressive strengths
above 60 MPa with the addition of 25% MK to NP. They add that
the setting time of the material is diminished by increasing the
percentage of added MK (500 min-5% MK vs. 160 min-25% MK).
Robayo-Salazar et al. [42] reported compressive strengths up to
44.9 MPa at 28 days of curing (25 °C) with the addition of 20%
MK, but noted that the 100% NP mixture did not harden at room
temperature and that heat curing (70 °C) was required. Adjust-
ments in the Na2O/Al2O3 ratio allow strengths for this same mix-
ture (20% MK) of up to 68.7 MPa to be obtained at 28 days of
curing. The microstructural characterization showed that MK pro-
motes the dissolution and subsequent participation in the geopoly-
merization processes of Si- and Al-rich phases present in NP.
Nadoushan and Ramezanianpour [66] reported strengths on the
order of 147.1 MPa (28 days at 25 °C) with the addition of 5% GBFS,
but it is worth mentioning that the NP used in that study was very
reactive and able to develop strengths on the order of 127.4 MPa
(100% NP) under the same activation conditions. Robayo-Salazar
et al. [21] reported increases of 143% in the heat of reaction
(48 h) with the addition of 30% GBFS and at the same time a reduc-
tion of the final setting time of the mixture at 111 min, versus
851 min for the blend with 100% NP; these results demonstrate
the effect of GBFS on the reaction kinetics of these AACs based
on NPs of moderate reactivity. In a later study, Robayo-Salazar
et al. [62] showed that there is a physico-chemical synergy
between the NP and the added GBFS that allows the achievement
of a superior mechanical performance (122 MPa at 90 days at
25 °C) to that reached by the system with 100%-GBFS (97 MPa).
They also report a decrease of the total porosity from 12.6% in
the 100%-NP mixture to 6.2% in the 70% NP-30% GBFS mixture
and a refinement of the meso- and micro-porosity of the AAC,
defined as the fraction of pores 0.01–0.1 and 0.01 lm in diame-
ter, which corroborates the mechanical performances obtained.
Microstructural analysis demonstrates how the presence of GBFS
in the mixture promotes the formation of C-S-H-type hydrates that
interact over time with N-A-S-H-type gels, resulting in the forma-
tion of gels of intermediate (N,C)-A-S-H and C-A-S-H compositions
(Dreierketten type structure), with higher calcium and aluminium
contents, which also explain the mechanical behaviours of these
mixtures (Fig. 4).
On the other hand, Allahverdi et al. [74] described how the
addition of 5% by weight of GBFS reduces or controls efflorescence
phenomena, guaranteeing a strength of 36 MPa at 28 days of cur-
ing (25 °C). Kani et al. [59] reported similar mechanical perfor-
mances and added that the addition of small amounts (<8%) of
MK and three types of CAC decrease the leaching of free alkalis
as a marker of efflorescence control and increase the content of
Si and Al soluble in the mixture, obtaining strengths above
70 MPa. Vafaei and Allahverdi [76] also reported mechanical bene-
fits (65 MPa) by incorporating CAC in amounts between 8 and
24% by weight. Their analysis is based on an increase in the content
of CaO and reactive Al2O3 up to 74% (24% CAC). The free alkali
 R.A. Robayo-Salazar, R. Mejía de Gutiérrez / Construction and Building Materials 189 (2018) 109–118
Fig. 4. Effects of the incorporation of GBFS (30% by weight) on alkaline activation (NaOH + Na2SiO3) of an NP of Colombian origin: (a) compressive strength (CS) (28 days
curing); (b) evolution of heat of reaction and total heat (25 °C); (c) peak region associated with C-A-S-H gel; (d) composition of the reaction products (SEM-EDS) (30% GBFS
mix). Source: [62].
content (Na2O) was decreased with the addition of CAC, which in
general shows an increase in the reaction rate of NP. The addition
of CAC also promoted an increase in reaction heat as an indicator of
the reaction kinetics, causing in turn a reduction of the final setting
time of the mixture to values of 75 min (24% CAC) versus 320 min
for the control mixture (0% CAC).
In general, the results discussed here demonstrate how the addi-
tion of sources of reactive Al2O3 and calcium in the synthesis of
‘‘alkali-activated binary cements” based on NPs of moderate or low
reactivity can make a positive contribution. An indicator of this is
the reduction of setting times and increases in the heats of reaction
and strengths at early ages, allowing at replacement of the hydro-
thermal curing processes, which were mentioned previously as
being necessary for NPs of low reactivity, by the addition of small
fractions (5–30%) of modifier minerals, especially MK or GBFS. How-
ever, one aspect that should be emphasised is that the location of the
NP natural deposit does not always coincide with the origin of the
minerals or industrial by-products used as modifiers of composition.
According to Djobo et al. [44], this difference can generate a logistic
cost that would compromise sustainable production (economically
and environmentally) of this type of materials on an industrial scale;
thus, this should be taken into account, or alternative and locally
available materials should be evaluated.
4. Durability of natural volcanic pozzolan-based alkali activated
materials
Several authors have reported that, in general, the chemical
durability (acids and sulphates) of AACs is high relative to OPC
[19,50,84–89]. However, until now, its performance against car-
bonation, freeze-thaw cycles, possible alkali–aggregate reaction,
chloride ion permeability and susceptibility of reinforcing steel to
corrosion is not clear due in large part to the lack of standards
115
designed to assess the durability of AACs, that currently require
used of test methods and limits established for the OPC, which
leads to confusing results. In this respect, RILEM and ASTM com-
mittees have been formed in recent years to work on the standard-
ization of test methods for alkali-activated materials. Another
aspect that hinders consensus on such performance is variability
in the mix designs used and, therefore, also the reported results
and in the case of NP-based AACs, durability reports are even scar-
cer [41,90–92].
In a first report, Bondar et al. [91] evaluated the oxygen and
chloride permeability of alkaline-activated NP-based concretes
with a solution of KOH + Na2SiO3. The results reported show that
NP-based concrete is 10–30% less permeable to oxygen (O2) than
an OPC concrete with the lowest permeability achieved by reduc-
ing the water/binder ratio (w/b: 0.45 vs. 0.55). The authors also
mentioned that applying a heat treatment (20–60 °C) promotes a
stronger (11.2–39.7 MPa) and less porous structure, which makes
the material less permeable. On the other hand, the authors
described how the accelerated method for evaluating chloride-
ion permeability based on ASTM C1202 (60 V DC for 6 h) gave
deceptively high (moderate to high permeability) results for con-
crete based on NPs. According to the authors, this could be attrib-
uted to the very high concentration of alkali ions in the pore
solution that promoted greater electrical conductivity through
the alkaline-activated concrete. In a later study, Bondar et al. [90]
evaluated the resistance to sulphates (2.5% Na2SO4 and 2.5%
MgSO4) of this same material. Their results showed a maximum
expansion after 6 months of immersion and a maximum loss of
strength after 2 years of immersion of 0.074 and 19.5%,
respectively.
Ghafoori et al. [41] evaluated the permeability of oxygen (O2)
and the permeability and diffusion of chloride ions in mortars
based on an NP activated with NaOH solution at concentrations of
116 R.A. Robayo-Salazar, R. Mejía de Gutiérrez / Construction and Building Materials 189 (2018) 109–118
2.5, 5, 7.5, 10 and 12.5 M, using activator/binder ratios of 0.50, 0.54
and 0.58. The authors agreed with Bondar et al. [91] that the total
loads, after the permeability test (60 V DC), were too high (i.e., they
gave misleading results). For this reason, they modified the method,
and the tests were performed using 10 V. However, the new results
still reflected high permeability values, despite the use of a lower
voltage. In addition, a rapid migration of chloride ions revealed that
permeability (presented as penetrated depth, diffusion coefficient,
and penetrated depth per volt-hour) decreased considerably with
increasing molarity of the NaOH solution and the reduction of the
activator/binder ratio (with similar patterns for the absorption
and volume of permeable pores). There was an average reduction
of 14.1 and 11.4% in the depth of the penetrated chloride when
the activator/binder ratio was reduced from 0.58 to 0.54 and from
0.54 to 0.50, respectively. The improvements were more significant
when the NaOH concentration increased. The depth of the
penetrated chloride was reduced by 37, 51, 52 and 20%, when the
molarity of the solution increased from 2.5 to 5, 5 to 7.5, 7.5 to 10
and 10 to 12.5 M, respectively.
Djobo et al. [92] evaluated the resistance to sulfuric acid (5%
H2SO4) of mortars cured at 27 and 80 °C based on an alkaline-
activated NP with a solution of NaOH + Na2SiO3. The results
showed that mortars cured at 27 °C exhibited better performance
than mortar cured at 80 °C due to a difference in microstructure
and pore connectivity. It seems that the curing process (80 °C) pro-
moted a more open porosity due to greater loss of moisture during
the hardening of the mortar. After 180 days of exposure to the acid
solution (5% H2SO4), the mortars exhibited losses of compression
strength of 24 and 60% and weights of 3.5 and 3.1% for mortars
cured at 27 and 80 °C, respectively. Microstructural analysis after
exposure revealed the formation of gypsum as a secondary phase
due to the reaction between the sulfuric acid and the calcium in
the geopolymer gel. The authors also reported that the presence
of a Na-rich gel reduces the pH of the system through an acid-
base reaction and that this slows down the gypsum-formation pro-
cess. This means that the behaviour of the material is governed not
only by its permeability (i.e., porous structure) but also by the
composition of the gels that compose it.
These results are limited and reveal the need for improved eval-
uation of the chemical resistance of NP-based AACs in order to be
confident about their performance in different aggressive environ-
ments (e.g., in sulphates and acids). The chloride ion permeability
results reported so far are contradictory and confusing. Beyond
these features, no studies to date have been reported involving
other characteristics of the durability of these materials, such as
susceptibility to carbonation, resistance to freeze–thaw cycles,
alkali–aggregate reactions and stability of the reinforcing steel
(i.e., corrosion).
5. Conclusions
Although the information on the production of AAM materials
based on natural Pozzolans presented in this review has shown
an appreciable number of studies developed by different research-
ers on a global scale, it should be noted that:
– Most of these studies have been carried out in pastes, so it is
necessary to evaluate these results in mixtures of concrete.
– Methodologies of mixing designs, appropriate to materials
based on volcanic pozzolans and their corresponding binary
mixtures using calcium and alumina correctors, have not been
reported.
– Studies on the rheology of mixtures and the use of additives
that improve them have not been reported.
– There are no studies with alternative activators of low environ-
mental impact.
– Studies of hybrid materials, where high content of volcanic poz-
zolan low percentages of Portland cement are used, are scarce.
– The information available on the durability of AAM based on
volcanic pozzolans is very limited and some results obtained
have generated controversies.
– The life cycle and production cost analysis reports of AAM based
on volcanic pozzolans that sustain its environmental and eco-
nomic advantages are limited.
6. Future challenges and opportunities
Undoubtedly, the use of NPs as a base material for the sustain-
able production of AACs is emerging as the most commercially and
industrially viable option in the foreseeable future. However, stud-
ies that support this real possibility are still scarce, and future
research should emphasise the following factors:
 Validation of mix designs with a wider range (sources) of NPs
worldwide.
 Use of materials as an alternative to MK or GBFS as mineral
modifiers or supplemental sources of reactive Al2O3 and cal-
cium for NPs of low reactivity, but which develop equal or supe-
rior strength at early ages.
 Use of alternative and solid activators (Na2CO3 or Na2SO4) with
lower carbon footprints and costs than the NaOH/KOH or Na2-
SiO3 used at present.
 Development of ‘‘hybrid cements” (OPC  30%) that have roused
the interest of the cement industry (i.e., commercial partners for
future introduction to the market).
 Rigorous studies of durability (e.g., susceptibility to carbona-
tion, resistance to freeze-thaw cycles, chemical resistance (to
acids and sulphates), alkali–aggregate reactions, chloride ion
permeability and stability of reinforcing steel (i.e., corrosion))
and development of suitable standard tests.
 Development of value-added applications or special classifica-
tions of materials developed based on their performance;
 Life cycle analysis (LCA), including the impacts associated with
the exploitation of NP deposits; and
 Analysis of costs at the industrial level, including the logistic
cost of the exploitation of NPs vs. OPC production.
7. Final comments
Alkali activated materials represent a line of research of great
interest worldwide, and the number of studies and publications
are growing. Despite this global interest, it is believed that current
and future research should focus on overcoming the challenges
that this technology faces with regard to its application at an
industrial level because these materials have demonstrated for
decades that they may be suitable for engineering applications of
high impact at the environmental (low-CO2-emission materials)
and technological (high-performance materials) levels. One of the
barriers to industrial development is the scarcity of studies on truly
available and sustainable raw materials (both precursors and acti-
vators). This review shows that global NPs deposits can be consid-
ered as a realistic alternative for the production of alkali activated
materials in the foreseeable future and highlights the key features
that need to be investigated to make these efforts a reality.
Conflict of interest
We declare no conflict of interest.
 R.A. Robayo-Salazar, R. Mejía de Gutiérrez / Construction and Building Materials 189 (2018) 109–118
Acknowledgements
The authors, members of the Composite Materials Group
(GMC), thank the University of Valle (Cali, Colombia), the Center
of Excellence of Novel Materials (CENM) and Colciencias (PUZO-
GEOH project contract No. 0484-2013) for the support received
in the investigation of NPs as raw material for the production of
alkali-activated materials in Colombia. R. Robayo-Salazar thanks
Colciencias for the support received in the Call No. 617 of 2013
for the training of doctors in Colombia.
References
[1] C. Shi, A.F. 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.
[2] J.S.J. Van Deventer, J.L. Provis, P. Duxson, D.G. Brice, Chemical research and
climate change as drivers in the commercial adoption of alkali activated
materials, Waste Biomass Valorization. 1 (2010) 145–155, https://doi.org/
10.1007/s12649-010-9015-9.
[3] K.A. Komnitsas, Potential of geopolymer technology towards green buildings
and sustainable cities, Proc. Eng. 21 (2011) 1023–1032, https://doi.org/
10.1016/j.proeng.2011.11.2108.
[4] R. Robayo-salazar, J. Mejía-arcila, R. Mejía de Gutiérrez, E. Martínez, Life cycle
assessment (LCA) of an alkali-activated binary concrete based on natural
volcanic pozzolan: a comparative analysis to OPC concrete, Constr. Build.
Mater. 176 (2018) 103–111, https://doi.org/10.1016/
j.conbuildmat.2018.05.017.
[5] B.C. McLellan, R.P. Williams, J. Lay, A. Van Riessen, G.D. 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.
[6] L. Szabo, I. Hidalgo, J.C. Ciscar, A. Soria, CO2 emission trading within the
European Union and Annex B countries: the cement industry case, Energy
Policy. 34 (2006) 72–87, https://doi.org/10.1016/j.enpol.2004.06.003.
[7] L.K. Turner, F.G. 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.
[8] C. Ouellet-Plamondon, G. Habert, Life cycle assessment (LCA) of alkali-
activated cements and concretes, in: Handb. Alkali-Activated Cem. Mortars
Concr., 2015, pp. 663–686. http://doi.org/10.1533/9781782422884.5.663.
[9] V.D. Glukhovsky, G. Rostovskaja, G.V. Rumyna, High strength slag-alkaline
cements, in: 7th Int. Congr. Chem. Cem. vol. 3, 1980, pp. 164–168.
[10] J. Davidovits, Properties of Geopolymer Cements, First Int. Conf. Alkaline Cem.
Concr., 1994, pp. 131–149.
[11] C. Shi, M. Tang, X. Wu, Research on alkali-activated cementitious systems in
China: a review, Adv. Cem. Res. 5 (1993) 1–7, https://doi.org/10.1680/
adcr.1993.5.17.1.
[12] F. Puertas, Cementos de escorias activadas alcalinamente: Situación actual y
perspectivas de futuro, Mater. Construcción. 45 (1995) 53–64, https://doi.org/
10.3989/mc.1995.v45.i239.553.
[13] J.L. Provis, J.S.J. van Deventer, Geopolymers: structures, processing, Prop. Ind.
Appl. (2009), https://doi.org/10.1533/9781845696382.
[14] J.S.J. Van Deventer, J.L. Provis, P. Duxson, Technical and commercial progress in
the adoption of geopolymer cement, Miner. Eng. 29 (2012) 89–104, https://
doi.org/10.1016/j.mineng.2011.09.009.
[15] M. Ahmaruzzaman, A review on the utilization of fly ash, Prog. Energy
Combust. Sci. 36 (2010) 327–363, https://doi.org/10.1016/j.pecs.2009.11.003.
[16] J.M. Paris, J.G. Roessler, C.C. Ferraro, H.D. DeFord, T.G. Townsend, A review of
waste products utilized as supplements to Portland cement in concrete, J.
Clean. Prod. (2015), https://doi.org/10.1016/j.jclepro.2016.02.013.
[17] M.R. Karim, M.F.M. Zain, M. Jamil, F.C. Lai, Fabrication of a non-cement binder
using slag, palm oil fuel ash and rice husk ash with sodium hydroxide, Constr.
Build. Mater. 49 (2013) 894–902, https://doi.org/10.1016/
j.conbuildmat.2013.08.077.
[18] B.L. Damineli, F.M. Kemeid, P.S. Aguiar, V.M. John, Measuring the eco-efficiency
of cement use, Cem. Concr. Compos. 32 (2010) 555–562, https://doi.org/
10.1016/j.cemconcomp.2010.07.009.
[19] J.L. Provis, Alkali-activated materials, Cem. Concr. Res. (2016), https://doi.org/
10.1016/j.cemconres.2017.02.009.
[20] C. Ruiz-Santaquiteria, A. Fernández-Jiménez, J. Skibsted, A. Palomo, Clay
reactivity: production of alkali activated cements, Appl. Clay Sci. 73 (2013) 11–
16, https://doi.org/10.1016/j.clay.2012.10.012.
[21] R.A. Robayo-Salazar, R. Mejía De Gutiérrez, M. Gordillo, Natural pozzolan-and
granulated blast furnace slag-based binary geopolymers, Mater. Constr. 66
(2016), https://doi.org/10.3989/mc.2016.03615 e077.
[22] M. Ibrahim, M.A. Megat Johari, M.K. Rahman, M. Maslehuddin, Effect of
alkaline activators and binder content on the properties of natural pozzolan-
based alkali activated concrete, Constr. Build. Mater. 147 (2017) 648–660,
https://doi.org/10.1016/j.conbuildmat.2017.04.163.
117
[23] P.N. Lemougna, K. Wang, Q. Tang, A.N. Nzeukou, N. Billong, Review on the use
of volcanic ashes for engineering applications, Resour. Conserv. Recycl. 137
(2018) 177–190, https://doi.org/10.1016/j.resconrec.2018.05.031.
[24] S. Shoji, R. Dahlgren, M. Nanzyo, Terminology, Concepts and Geographic
Distribution of Volcanic Ash Soils, in: Dev. Soil Sci., 1993, pp. 1–5. http://doi.
org/10.1016/S0166-2481(08)70262-9.
[25] A.R. Pourkhorshidi, M. Najimi, T. Parhizkar, F. Jafarpour, B. Hillemeier,
Applicability of the standard specifications of ASTM C618 for evaluation of
natural pozzolans, Cem. Concr. Compos. 32 (2010) 794–800, https://doi.org/
10.1016/j.cemconcomp.2010.08.007.
[26] T. Takahashi, S. Shoji, Distribution and classification of volcanic ash soils, Glob.
Environ. Res. 6 (2002) 83–97. http://ns.airies.or.jp/publication/ger/pdf/06-2-
10.pdf.
[27] A. Lizcano, M.C. Herrera, Suelos derivados de cenizas volcánicas en colombia,
Rev. Int. Desastr. Nat. Accid. e Infraestruct. Civ. 6 (2006) 167–198.
[28] R. Snellings, G. Mertens, J. Elsen, Supplementary cementitious materials, Rev.
Mineral. Geochem. 74 (2012) 211–278, https://doi.org/10.2138/
rmg.2012.74.6.
[29] M. Nanzyo, S. Shoji, R. Dahlgren, Volcanic ash soils - genesis, properties and
utilization, Dev. Soil Sci. 21 (1993) 189–207, https://doi.org/10.1016/S0166-
2481(08)70268-X.
[30] M. Nanzyo, R. Dahlgren, S. Shoji, Chemical characteristics of volcanic ash soils,
Dev. Soil Sci. 21 (1993) 145–187, https://doi.org/10.1016/S0166-2481(08)
70267-8.
[31] S. Shoji, R. Dahlgren, M. Nanzyo, Classification of volcanic ash soils, Dev. Soil
Sci. 21 (1993) 73–100, https://doi.org/10.1016/S0166-2481(08)70265-4.
[32] A. Allahverdi, K. Mehrpour, E. Najafikani, Investigating the possibility of
utilizing pumice-type natural pozzonal in production of geopolymer cement,
Ceram. - Silikaty. 52 (2008) 16–23.
[33] D. Bondar, C.J. Lynsdale, N.B. Milestone, N. Hassani, A.A. Ramezanianpour,
Effect of heat treatment on reactivity-strength of alkali-activated natural
pozzolans, Constr. Build. Mater. 25 (2011) 4065–4071, https://doi.org/
10.1016/j.conbuildmat.2011.04.044.
[34] P.N. Lemougna, K.J.D. MacKenzie, U.F.C. Melo, Synthesis and thermal
properties of inorganic polymers (geopolymers) for structural and refractory
applications from volcanic ash, Ceram. Int. 37 (2011) 3011–3018, https://doi.
org/10.1016/j.ceramint.2011.05.002.
[35] H.T. Kouamo, A. Elimbi, J.A. Mbey, C.J.N. Sabouang, D. Njopwouo, The effect of
adding alumina-oxide to metakaolin and volcanic ash on geopolymers
products: a comparative study, Constr. Build. Mater. 35 (2012) 960–969,
https://doi.org/10.1016/j.conbuildmat.2012.04.023.
[36] J. Moon, S. Bae, K. Celik, S. Yoon, K.H. Kim, K.S. Kim, P.J.M. Monteiro,
Characterization of natural pozzolan-based geopolymeric binders, Cem. Concr.
Compos. 53 (2014) 97–104, https://doi.org/10.1016/j.
cemconcomp.2014.06.010.
[37] H. Takeda, S. Hashimoto, H. Kanie, S. Honda, Y. Iwamoto, Fabrication and
characterization of hardened bodies from Japanese volcanic ash using
geopolymerization, Ceram. Int. 40 (2014) 4071–4076, https://doi.org/
10.1016/j.ceramint.2013.08.061.
[38] R.H. Haddad, O. Alshbuol, Production of geopolymer concrete using natural
pozzolan: a parametric study, Constr. Build. Mater. 114 (2016) 699–707,
https://doi.org/10.1016/j.conbuildmat.2016.04.011.
[39] A. Nikolov, I. Rostovsky, H. Nugteren, Geopolymer materials based on natural
zeolite, Case Stud. Constr. Mater. 6 (2017) 198–205, https://doi.org/10.1016/j.
cscm.2017.03.001.
[40] D.M. González-García, L. Téllez-Jurado, F.J. Jiménez-Álvarez, H. Balmori-
Ramírez, Structural study of geopolymers obtained from alkali-activated
natural pozzolan feldspars, Ceram. Int. 43 (2017) 2606–2613, https://doi.org/
10.1016/j.ceramint.2016.11.070.
[41] N. Ghafoori, M. Najimi, B. Radke, Natural Pozzolan-based geopolymers for
sustainable construction, Environ. Earth Sci. 75 (2016), https://doi.org/
10.1007/s12665-016-5898-5.
[42] R.A. Robayo-Salazar, R. Mejía de Gutiérrez, F. Puertas, Effect of metakaolin on
natural volcanic pozzolan-based geopolymer cement, Appl. Clay Sci. 132–133
(2016) 491–497, https://doi.org/10.1016/j.clay.2016.07.020.
[43] M. Nakagawa, T. Ohba, Minerals in Volcanic Ash 1: Primary Minerals and
Volcanic Glass, Glob. Environ. Res. (2002) 41–51. http://www.airies.or.jp/
publication/ger/pdf/06-2-06.pdf.
[44] J.N.Y. Djobo, A. Elimbi, H.K. Tchakouté, S. Kumar, Volcanic ash-based
geopolymer cements/concretes: the current state of the art and perspectives,
Environ. Sci. Pollut. Res. 24 (2017) 4433–4446, https://doi.org/10.1007/
s11356-016-8230-8.
[45] R. Dahlgren, S. Shoji, M. Nanzyo, Mineralogical characteristics of volcanic ash
soils, Dev. Soil Sci. 21 (1993) 101–143, https://doi.org/10.1016/S0166-2481
(08)70266-6.
[46] E.N. Kani, A. Allahverdi, Effect of chemical composition on basic engineering
properties of inorganic polymeric binder based on natural pozzolan, Ceram. -
Silikaty. 53 (2009) 195–204.
[47] P.N. Lemougna, U.F. Chinje Melo, M.P. Delplancke, H. Rahier, Influence of the
chemical and mineralogical composition on the reactivity of volcanic ashes
during alkali activation, Ceram. Int. 40 (2014) 811–820, https://doi.org/
10.1016/j.ceramint.2013.06.072.
[48] R. Çetintasß, S. Soyer-Uzun, Relations between structural characteristics and
compressive strength in volcanic ash based one–part geopolymer systems, J.
Build. Eng. 20 (2018) 130–136, https://doi.org/10.1016/j.jobe.2018.07.011.
118 R.A. Robayo-Salazar, R. Mejía de Gutiérrez / Construction and Building Materials 189 (2018) 109–118
[49] A. Palomo, P. Krivenko, I. Garcia-Lodeiro, E. Kavalerova, O. Maltseva, A.
Fernández-Jiménez, A review on alkaline activation: new analytical
perspectives, Mater. Construcción. 64 (2014), https://doi.org/10.3989/
mc.2014.00314 e022.
[50] P. Krivenko, Why alkaline activation – 60 years of the theory and practice of
alkali-activated materials, J. Ceram. Sci. Technol. (2017) 323–334, https://doi.
org/10.4416/JCST2017-00042.
[51] H. Tchakoute Kouamo, J.A. Mbey, A. Elimbi, B.B. Kenne Diffo, D. Njopwouo,
Synthesis of volcanic ash-based geopolymer mortars by fusion method: effects
of adding metakaolin to fused volcanic ash, Ceram. Int. 39 (2013) 1613–1621,
https://doi.org/10.1016/j.ceramint.2012.08.003.
[52] J.N. Yankwa Djobo, A. Elimbi, H.K. Tchakouté, S. Kumar, Mechanical activation
of volcanic ash for geopolymer synthesis: effect on reaction kinetics, gel
characteristics, physical and mechanical properties, RSC Adv. 6 (2016) 39106–
39117, https://doi.org/10.1039/C6RA03667H.
[53] B.I. Djon Li Ndjock, A. Elimbi, M. Cyr, Rational utilization of volcanic ashes
based on factors affecting their alkaline activation, J. Non. Cryst. Solids 463
(2017) 31–39, https://doi.org/10.1016/j.jnoncrysol.2017.02.024.
[54] D. Bondar, C.J. Lynsdale, N.B. Milestone, Simplified model for prediction of
compressive strength of alkali-activated natural pozzolans, J. Mater. Civ. Eng.
24 (2012) 391–400, https://doi.org/10.1061/(ASCE)MT.1943-5533.0000400.
[55] H. Kouamo Tchakoute, A. Elimbi, B.B. Diffo Kenne, J.A. Mbey, D. Njopwouo,
Synthesis of geopolymers from volcanic ash via the alkaline fusion method:
effect of Al2O3/Na2O molar ratio of soda-volcanic ash, Ceram. Int. 39 (2013)
269–276, https://doi.org/10.1016/j.ceramint.2012.06.021.
[56] E.A. Ortega, C. Cheeseman, J. Knight, M. Loizidou, Properties of alkali-activated
clinoptilolite, Cem. Concr. Res. 30 (2000) 1641–1646, https://doi.org/10.1016/
S0008-8846(00)00331-8.
[57] E.N. Kani, A. Allahverdi, Effects of curing time and temperature on strength
development of inorganic polymeric binder based on natural pozzolan, J.
Mater. Sci. 44 (2009) 3088–3097, https://doi.org/10.1007/s10853-009-3411-1.
[58] D. Bondar, C.J. Lynsdale, N.B. Milestone, N. Hassani, A.A. Ramezanianpour,
Effect of type, form, and dosage of activators on strength of alkali-activated
natural pozzolans, Cem. Concr. Compos. 33 (2011) 251–260, https://doi.org/
10.1016/j.cemconcomp.2010.10.021.
[59] E. Najafi, A. Allahverdi, J.L. Provis, Efflorescence control in geopolymer binders
based on natural pozzolan, Cem. Concr. Compos. 34 (2012) 25–33, https://doi.
org/10.1016/j.cemconcomp.2011.07.007.
[60] H.K. Tchakoute, A. Elimbi, E. Yanne, C.N. Djangang, Utilization of volcanic ashes
for the production of geopolymers cured at ambient temperature, Cem. Concr.
Compos. 38 (2013) 75–81, https://doi.org/10.1016/j.cemconcomp.2013.03.010.
[61] J.N.Y. Djobo, A. Elimbi, H.K. Tchakouté, S. Kumar, Reactivity of volcanic ash in
alkaline medium, microstructural and strength characteristics of resulting
geopolymers under different synthesis conditions, J. Mater. Sci. 51 (2016)
10301–10317, https://doi.org/10.1007/s10853-016-0257-1.
[62] R.A. Robayo-Salazar, M. de Gutiérrez, F. Puertas, Study of synergy between a
natural volcanic pozzolan and a granulated blast furnace slag in the
production of geopolymeric pastes and mortars, Constr. Build. Mater. 157
(2017) 151–160, https://doi.org/10.1016/j.conbuildmat.2017.09.092.
[63] M. Taxiarchou, D. Panias, C. Panagiotopoulou, A. Karalis, C. Dedeloudis, Study
on the suitability of volcanic amorphous aluminosilicate rocks (Perlite) for the
synthesis of geopolymer-based concrete, Geopolym. Bind. Syst. STP 1566
(2013) 34–53, https://doi.org/10.1520/STP156620120077.
[64] E.N. Kani, A. Allahverdi, Investigating shrinkage changes of natural pozzolan
based geopolymer cement paste, Iran. J. Mater. Sci. Eng. 8 (2011) 50–60.
[65] D. Bondar, C.J. Lynsdale, N.B. Milestone, N. Hassani, A.A. Ramezanianpour,
Engineering properties of alkali activated natural pozzolan concrete, ACI
Mater. J. 108 (2011) 64–72.
[66] M. Jafari Nadoushan, A.A. Ramezanianpour, The effect of type and
concentration of activators on flowability and compressive strength of
natural pozzolan and slag-based geopolymers, Constr. Build. Mater. 111
(2016) 337–347, https://doi.org/10.1016/j.conbuildmat.2016.02.086.
[67] P.N. Lemougna, U.F. Chinje Melo, M.P. Delplancke, H. Rahier, Influence of the
activating solution composition on the stability and thermo-mechanical
properties of inorganic polymers (geopolymers) from volcanic ash, Constr.
Build. Mater. 48 (2013) 278–286, https://doi.org/10.1016/
j.conbuildmat.2013.06.089.
[68] F. Puertas, M. Torres-Carrasco, Use of glass waste as an activator in the
preparation of alkali-activated slag. Mechanical strength and paste
characterisation, Cem. Concr. Res. 57 (2014) 95–104, https://doi.org/
10.1016/j.cemconres.2013.12.005.
[69] M. Torres-carrasco, J.G. Palomo, F. Puertas, Sodium silicate solutions from
dissolution of glass wastes. Statistical analysis, Mater. Construcción. 64 (2014)
1–14, https://doi.org/10.3989/mc.2014.05213.
[70] J.M. Mejía, R. Mejía de Gutiérrez, C. Montes, Rice husk ash and spent
diatomaceous earth as a source of silica to fabricate a geopolymeric binary
binder, J. Clean. Prod. 118 (2016) 133–139, https://doi.org/10.1016/j.
jclepro.2016.01.057.
[71] M.A. Villaquirán-Caicedo, R. Mejía de Gutiérrez, S. Sulekar, C. Davis, J.C. Nino,
Thermal properties of novel binary geopolymers based on metakaolin and
alternative silica sources, Appl. Clay Sci. 118 (2015) 276–282, https://doi.org/
10.1016/j.clay.2015.10.005.
[72] A. Fernández-Jiménez, A. Palomo, I. Sobrados, J. Sanz, The role played by the
reactive 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.
[73] P. Duxson, J.L. Provis, Designing precursors for geopolymer cements, J. Am.
Ceram. Soc. 91 (2008) 3864–3869, https://doi.org/10.1111/j.1551-
2916.2008.02787.x.
[74] A. Allahverdi, E. Kani, M. Yazdanipour, Effects of blast furnance slag on natural
pozzolan- based geopolymer cement, Ceramics-Silickáty. 55 (2011) 68–78.
[75] D. Bondar, C.J. Lynsdale, N.B. Milestone, N. Hassani, A.A. Ramezanianpour,
Effect of adding mineral additives to alkali-activated natural pozzolan paste,
Constr. Build. Mater. 25 (2011) 2906–2910, https://doi.org/10.1016/
j.conbuildmat.2010.12.031.
[76] M. Vafaei, A. Allahverdi, Influence of calcium aluminate cement on
geopolymerization of natural pozzolan, Constr. Build. Mater. 114 (2016)
290–296, https://doi.org/10.1016/j.conbuildmat.2016.03.204.
[77] E. Najafi Kani, A. Allahverdi, J.L. Provis, Calorimetric study of geopolymer
binders based on natural pozzolan, J. Therm. Anal. Calorim. 127 (2017) 2181–
2190, https://doi.org/10.1007/s10973-016-5850-7.
[78] J.N.Y. Djobo, L.N. Tchadjié, H.K. Tchakoute, B.B.D. Kenne, A. Elimbi, D.
Njopwouo, Synthesis of geopolymer composites from a mixture of volcanic
scoria and metakaolin, J. Asian Ceram. Soc. 2 (2014) 387–398, https://doi.org/
10.1016/j.jascer.2014.08.003.
[79] F. Puertas, M. Palacios, H. Manzano, J.S. Dolado, A. Rico, J. Rodríguez, A model
for the C-A-S-H gel formed in alkali-activated slag cements, J. Eur. Ceram. Soc.
31 (2011) 2043–2056, https://doi.org/10.1016/j.jeurceramsoc.2011.04.036.
[80] A. Fernández-Jiménez, F. Puertas, I. Sobrados, J. Sanz, Structure of calcium
silicate hydrates formed in alkaline-activated slag: influence of the type of
alkaline activator, J. Am. Ceram. Soc. 86 (2003) 1389–1394, https://doi.org/
10.1111/j.1151-2916.2003.tb03481.x.
[81] I. Garcia-Lodeiro, A. Palomo, A. Fernández-Jiménez, D.E. MacPhee,
Compatibility studies between N-A-S-H and C-A-S-H gels. Study in the
ternary diagram Na2O-CaO-Al2O3-SiO2-H2O, Cem. Concr. Res. 41 (2011)
923–931, https://doi.org/10.1016/j.cemconres.2011.05.006.
[82] M. Torres-Carrasco, F. Puertas, Alkaline activation of aluminosilicates as an
alternative to Portland cement: a review, Rom. J. Mater. 47 (2017) 3–15.
[83] I. Garcia-Lodeiro, S. Donatello, A. Fernández-Jiménez, Á. Palomo, Hydration of
hybrid alkaline cement containing a very large proportion of fly ash: a
descriptive model, Materials (Basel). 9 (2016), https://doi.org/10.3390/
MA9070605.
[84] F. Pacheco-Torgal, Z. Abdollahnejad, A.F. Camões, M. Jamshidi, Y. Ding,
Durability of alkali-activated binders: a clear advantage over Portland
cement or an unproven issue?, Constr Build. Mater. 30 (2012) 400–405,
https://doi.org/10.1016/j.conbuildmat.2011.12.017.
[85] S.A. Bernal, J.L. Provis, Durability of alkali-activated materials: progress and
perspectives, J. Am. Ceram. Soc. 97 (2014) 997–1008, https://doi.org/
10.1111/jace.12831.
[86] D. Bondar, C.J. Lynsdale, N.B. Milestone, Alkali-activated natural pozzolan
concrete as new construction material, ACI Mater. J. 110 (2013) 331–337,
https://doi.org/10.14359/51685667.
[87] S.A. Bernal, R. Mejía De Gutiérrez, J.L. Provis, Engineering and durability
properties of concretes based on alkali-activated granulated blast furnace slag/
metakaolin blends, Constr. Build. Mater. 33 (2012) 99–108, https://doi.org/
10.1016/j.conbuildmat.2012.01.017.
[88] J. Zhang, C. Shi, Z. Zhang, Z. Ou, Durability of alkali-activated materials in
aggressive environments: a review on recent studies, Constr. Build. Mater. 152
(2017) 598–613, https://doi.org/10.1016/j.conbuildmat.2017.07.027.
[89] J.L. Provis, A. Palomo, C. Shi, Advances in understanding alkali-activated
materials, Cem. Concr. Res. 78 (2015) 110–125, https://doi.org/10.1016/j.
cemconres.2015.04.013.
[90] D. Bondar, C.J. Lynsdale, N.B. Milestone, N. Hassani, Sulfate resistance of alkali
activated Pozzolans, Int. J. Concr. Struct. Mater. 9 (2015) 145–158, https://doi.
org/10.1007/s40069-014-0093-0.
[91] D. Bondar, C.J. Lynsdale, N.B. Milestone, N. Hassani, Oxygen and chloride
permeability of alkali-activated natural pozzolan concrete, ACI Mater. J. 109
(2012) 53–61.
[92] J.N. Yankwa Djobo, A. Elimbi, H. Kouamo Tchakoute, S. Kumar, Mechanical
properties and durability of volcanic ash based geopolymer mortars, Constr.
Build. Mater. 124 (2016) 606–614, https://doi.org/10.1016/
j.conbuildmat.2016.07.141.