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Why Alkaline Activation – 60 Years of the Theory and Practice of Alkali-

Activated Materials

Article in Journal of Ceramic Science and Technology · August 2017

DOI: 10.4416/JCST2017-00042

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 J. Ceram. Sci. Technol. 323-334 (2017)
DOI: 10.4416/JCST2017-00042
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© 2017 Göller Verlag

Review
Why Alkaline Activation – 60 Years of the Theory and
Practice of Alkali-Activated Materials
P. Krivenko *
Scientific Research Institute for Binders and Materials, Kyiv National University of
Construction and Architecture, Povitroflotskyi prospect 31, Kyiv 03037 Ukraine
received June 14, 2017; received in revised form August 1, 2017; accepted August 24, 2017

Abstract
Sixty years ago, just the idea of the presence of free alkalis in a cement matrix was considered by ordinary Portland
cement people to be absurd, and this was a basic postulate accepted in cement chemistry. In 1957, a scientist from Kyiv,
Ukraine (then, USSR), Victor Glukhovsky, put forward an assumption that was taken as a basis for development
and realization of a principally new class of cementitious materials, which first appeared under the name of “alkaline
cements” (nowadays also known under the general name of “alkali-activated cements”). The validity of these ideas is
confirmed by more than 60 years of evolutionary development and vast experience collected from the practical use
of these new materials in a variety of large-scale applications. The present review covers theoretical views on the role
played by alkali in the formation of cement stone structure. Examples of compositional build-up of alkali-activated
cementitious materials as a function of the quantity of the alkali and type of aluminosilicate component are reported,
as well as the findings of analysis of alkali-activated cement concrete structures.
Keywords: Alkaline activation, aluminosilicate, cement, concrete, durability, hydration products, terminology

I. Introduction relatively high solubility of the hydration products, and

low corrosion resistance in the presence of Ca(OH) 2 and
Alkali metal compounds were excluded from tradition-
3CaO⋅Al 2O 3⋅3CaSO 4⋅31H 2O. Above all, the production
al hydraulic cement components on account of their high
of Portland cement is associated with high consumption
solubility. At the same time, studies undertaken to reveal
of energy (7500 J/t), high carbon dioxide (CO 2)emissions
reasons for the excellent durability of ancient cements to-
(0.5 metric t/t) and the depletion of natural resources.
gether with the data collected on the stability and compo-
sition of natural minerals testified that this opinion was not That is why the cement science should move in the direc-
correct. tion of cement alternatives to OPCs.
According to data reported in references 1 – 7, excellent One such cement that appeared in the field over 60
durability of the ancient concrete structures was attributed years ago is a class of alkaline or alkali-activated cements
to the considerably greater quantities of alkali metal com- (AACs). This paper covers the theoretical principles laid
pounds contained in ancient cements compared to in con- down in the creation of these cements, history and experi-
temporary Portland cements. This was found to result in ence collected from large-scale applications.
the formation of a cement stone structure of alkaline alu-
minosilicate hydrate compounds – analogs of natural ze- II. Historical Aspects and Overview
olites along with calcium silicate hydrates. At the same First data about the possibility of producing a binder ma-
time, a strategy of global sustainable development prede- terial from granulated blast-furnace slag and caustic soda
termined the actions to be taken by the building materials in combination with slaked lime go back to 1895 8.
industry, in particular by the cement industry.
Later, in the 1930s, H. Kühl reported studies on the set-
Ordinary Portland cement has proven to be an excel-
ting behavior of mixtures of ground slag and a solution
lent building material, and concretes based on this ex-
of caustic potash 9. R. Feret reported on the necessity to
hibit good physico-mechanical properties and durability.
study slags as a cement component 10. In 1940, A. Purdon
However, when Portland cement is exposed to extreme
reported on the results of first extensive laboratory stud-
service conditions (high/low temperature, corrosive envi-
ies on cements without OPC clinker, consisting of slag and
ronments, radiation, etc.), its drawbacks become apparent,
caustic alkalis produced with a base and an alkaline salt 11.
resulting in poor performance. These drawbacks can be at-
Later, in 1957, a Soviet Union scientist Victor
tributed to the metastability of Portland cement hydration
Glukhovsky 12 was the first to discover the possibili-
products resulting from conversion of high-basicity cal-
ty of making binding materials using low-basic-calcium
cium hydrate in the low basicity of C 2SH into CSH(B),
or calcium-free aluminosilicates (clays) and solutions
* Corresponding author: [email protected] of alkali metals. He called these binders “soil cements”
324 Journal of Ceramic Science and Technology —P. Krivenko 2017

and “soil silicates” in order to reflect their similarity to first group of the periodic table – exhibited hydraulic bind-
natural minerals. Depending on the composition of their ing properties similar to those of alkaline earth metals (Mg,
constituent materials, the AACs were divided into two Ca, Sr, Ba) – the elements of the second group.
groups: alkaline (Me 2O-Me 2O 3-SiO 2-H 2O) and alka- The idea to use these compounds as cementitious sys-
line-alkaline earth (Me 2O-MeO-Me 2O 3-SiO 2-H 2O). As tems was, first of all, based on collected geological da-
a result, a variety of AACs have been formulated from ta that sodium- potassium- and calcium aluminosilicate
metallurgical slags, clays, aluminosilicate rocks, fuel ash- compounds, which are known to have higher stability
es and other constituents. Extensive research and devel- and resistance to atmospheric reagents, are present in the
opment of AACs and AAC-based concretes have been earth’s crust. Secondly, this idea was based on experimen-
initated since those times. In particular, Trief cements and tal observation that proved that alkali metal hydroxides
F-cements from Scandinavian countries (Forss) and al- and salts of alkali metals entered into interaction with
kali-activated blended cements are more recent examples clay minerals, aluminosilicate glasses and crystalline sub-
(J. Davidovits, D. Roy and M. Silsbee). stances of natural and artificial origin, with the formation
In the 1980s, J. Davidovits 13 published his results on of water-resistant alkaline and alkaline-alkaline earth alu-
making binders by mixing alkalis with a burnt mixture minosilicate hydration products that were analogs of nat-
of kaolinite, limestone and dolomite. He called these ural minerals of the zeolite and mica types 18.
binders “geopolymers” because their structure was simi-
lar to polymers. He has also registered several trademarks
(1) Alkalis in nature
such as Pyrament, Geopolycem and Geopolymite. These
materials belong to the alkaline binding system Me 2O- Based on geological data, the earth‘s crust contains a
Me 2O 3-SiO 2-H 2O, as proposed by V. Glukhovsky. large number of calcium, sodium or calcium-sodium alu-
In 1986, P. Krivenko published the results of his research minosilicate formations 19.
on the principles of regulation of technological and physi- Some sedimentary, stone-like rock formation processes
co-mechanical properties of AACs and ACC concretes 14. take place under temperatures and pressures close to those
R. Malek, D. Roy et al. 15 identified the alkali-activat- used in the production of materials from hydraulic ce-
ed cement-type materials as a matrix formed in the solid- ments and, hence, can be simulated in the building ma-
ification of certain radioactive wastes, while D. Roy and terials industry. For example, zeolites of sedimentary
C. Langton 16 showed some analogies of such materials origin, such as analcime Na[AlSi 2O 6]⋅H 2O, phillipsite
with ancient concretes. (K 2, Ca) [Al 2SiO 12]⋅4.5H 2O, mordenite (Ca, Na 2, K 2)
P. Krivenko 17 further showed that alkalis and alkali met- [Al 2Si 9O 22]⋅6H 2O, natrolite Na 2 [Al 2Si 3O 10]⋅2H 2O,
al salts, similar to silicates, aluminates and aluminosili- scolecite Ca[Al 2Si 3O 10]⋅2H 2O and other zeolites occur
cates, enter into reaction in an alkaline aqueous medium in residual soil as a result of low-temperature hydrother-
under conditions of high alkali concentration. Such in- mal reactions. Analcime, for instance, is formed at the
teraction takes place with clay minerals, aluminosilicate bottom of sea basins at temperatures below 30 °C as a
glasses of natural and artificial origin, in which calcium result of interaction between volcanic ash, which decom-
is absent, as well as with calcium-based cementitious sys- poses into a silicic acid and alumina, and alkali metal salt
tems in ambient (normal) conditions with the formation of dissolved in water. An occurrence of this or that type of
water-resistant alkaline or alkaline-alkaline earth alumi- zeolite depends upon the chemical composition of the
nosilicate hydrates, which are analogs of natural zeolites hydrothermal solutions. For example, chiefly calcium va-
and micas. rieties are known to occur in rich-calcium solutions. With
III. Why Alkaline Activation? the increase in concentrations of alkalis, the alkaline earth
cations are partially or completely replaced by sodium or
Alkalis play an important role in the processes of artifi-
potassium, resulting in the formation of zeolites of the
cial stone formation taking place in nature, they are found
alkaline and alkaline-alkaline earth composition.
in concrete of ancient structures and are contained in con-
temporary cements. Analysis of data on sedimentation processes showed
Less than a century ago, just the idea of the presence of that chemical decomposition of rocks under the action of
free alkali in a cement composition was considered absurd alkaline solutions depended upon their chemical and con-
by cement specialists and this was a basic postulate of the stituent compositions. Hydrated aluminosilicates: mus-
fundamentals for exhibiting hydraulic properties based on covite, sericite, zeolites, etc. are the products of chemical
mineral systems. The alkali metal compounds were ex- decomposition of widely found rocks of alkaline and al-
cluded from components of traditional hydraulic cemen- kaline-alkaline earth aluminosilicate compositions, such
titious systems because of their high solubility. as plagioclases and sodium-potassium feldspars. The most
At the same time, extensive studies undertaken to re- characteristic process of decomposition of plagioclases
veal reasons for the excellent durability of ancient concrete (alkaline-alkaline earth aluminosilicate hydrates) is the
structures in combination with data collected on the sta- process of sericitization – a replacement of plagioclases by
bility and composition of natural mineral formations tes- muscovite; that is a conversion of anhydrous aluminosil-
tified that this postulate was not correct. icates containing anorthite into alkaline aluminosilicate
V. Glukhovsky made an assumption (and this was a rev- hydrates.
olutionary discovery in cement science) that compounds Finally, as a result of interaction of the feldspar (R 2O
of alkali metals (Li, Na, K, Rb, Cs) – the elements of the ⋅Al 2O 3⋅6SiO 2⋅nH 2O) with water, two reactions that can
2017 Why Alkaline Activation – 60 Years of the Theory and Practice of Alkali-Activated Materials 325

be schematically represented as shown below can take and lime. In both cases, natural processes of metamor-
place (with approximation): phism lead to changes in the mineral hydration products as
a result of alkaline substances being introduced or removed
0.33(R2 O · 3Al2 O3 · 6SiO2 · mH2 O) by circulating overheated aqueous solutions. They are re-
+ 0.67(R2 O · 6SiO2 · xH2 O) or (1) flected in the removal or binding of alkalis, crystallization
of zeolites, hydromicas, micas, which under conditions
R2 O · Al2 O3 · 4SiO2 · 2H2 O + 2SiO2 · (n-2) H2 O. of thermal metamorphism tend to recrystallize later into
Their essence can be explained as hydration of the anhy- albite, orthoclase, feldspathoids and others.
drous alkaline aluminosilicates and formation of hydrates, Among a variety of phases that are formed, the zeo-
including aluminosilicates of the muscovite or analcime- lite-like Na-K-Ca aluminosilicate phases are the most
type. This process is similar to the process in Portland resistant to carbonation and to lowering of alkalini-
clinker mineral hydration. An assumption can be pro- ty of the pore liquid. At values 7 < pH < 9 they re-
posed that it may take place during hardening of the al- place such phases as, for example, calcium silicate hy-
kaline and alkaline-alkaline earth cementitious systems 19. drates Ca 2SiO 3O 8⋅5H 2O, (CaO) 0.833⋅SiO 2⋅(H 2O) 1.333,
According to their solubility in the weathering zone, the tacharanite (clinotobermorite) Ca 12Al 2Si 18O 33(OH) 36,
elements of alkali metal and alkaline earth metals can be apophyllite KCa 4(Si 4O 10) 2 OH⋅8H 2O, etc. 4.
arranged as follows: calcium (with the highest solubility), Worth mentioning is that a specific feature of the meta-
sodium and magnesium and, lastly, potassium. For exam- morphism stage is the higher pressures compared to those
ple, potassium feldspars tend to decompose more slow- used in the production of building materials, which is why
ly than the calcium and sodium ones, of which albite was simulating this process in practice is a complicated mat-
found to be the most stable mineral. For plagioclases, an ter. However, the work conducted by the scientific school
inverse relationship of resistance of the minerals to the in Kiev suggested simulation based on the use of alumi-
nosilicate substances of metastable structure and active al-
quantity of the anorthite component occurs: the calcium
kali metal non-silicate or silicate compounds in quantities
plagioclases decompose at faster rates.
required for the synthesis of alkaline aluminosilicate hy-
Alkaline aluminosilicate hydrates such as muscovite and
drates. Similar processes could be simulated in large vol-
paragonite exhibit increased resistance to weathering com-
umes and under curing regimes (temperatures and humid-
pared to calcium hydrates. These data provide proof of the
ity) used in the production of traditional Portland cement
higher durability of the AAC hydration products contain-
concretes.
ing hydrated sodium and potassium aluminosilicates. A
By summarizing the above, a conclusion could be drawn
trend to reduce the basicity of hydration products com-
that in the earth’s crust and on its surface, continuous
pared to initial unhydrated minerals is also a proof of the
stage-by-stage polymerization and depolymerization
analogy between the processes taking place in nature and
processes of silicate substances take place and are accom-
man-made conditions to produce alkaline and alkaline-al-
panied by mutual conversions of hydrated into unhydrat-
kaline earth aluminosilicate compositions. In the general
ed mineral systems and vice versa. They progress mainly
case, these processes have the following basic stages con- with participation of the alkali metal and alkaline earth
nected with changes in alkalinity of the environment: hy- metal oxides, resulting, similar to the processes of hydra-
dration of alkali metal and alkaline earth metals, and par- tion and hardening of cementitious building materials, in
tial replacement of alkalis and alkaline earth metals. With the synthesis of stone-like hydration products. These data
the ions of hydroxyl or hydroxon, the less alkaline, al- could be a prerequisite for the synthesis of analogs of nat-
most insoluble aluminosilicate hydrates of the R 2O⋅(1 – 3) ural aqueous sodium-potassium-calcium minerals based
Al 2O 3⋅(2 – 6)⋅nH 2O type and low basic alkaline earth sili- on hydration of alkaline-alkaline earth cementitious sys-
cate hydrates of the RO⋅SiO 2⋅nH 2O type as well as soluble tems. These are: alkaline-alkaline earth cements, which in
hydrates of the R(OH) 2, ROH, R 2O⋅SiO 2⋅nH 2O⋅Al 2O 3 the general case may contain slags, intrusive and effusive
⋅nH 2O types in amorphous or submicrocrystalline states rocks, clay minerals, silica, etc. In the process of interac-
can appear. tion of these substances with alkali metal hydroxides, the
Hydrothermal metamorphism which occurs in the processes of formation of minerals in the earth’s crust and
earth’s crust at relatively low temperatures and pressures stone-like rocks are replicated.
results in the processes of rock transformation accompa-
nied by hydration of the feldspar minerals and formation (2) Modeling of rock – mineral formation processes
of water-resistant and non-water-resistant alkaline hy- A scheme of the formation of sedimentary rocks based on
dration products. In their essence, they are similar to the rock weathering products was adopted for modeling 19.
processes taking place in the zone of sediment accumula- It was established that alkali metal hydroxides and salts
tion and to the hydration processes of cementitious build- of alkali metals produce in an aqueous medium an alkaline
ing materials. Along with this, the aqueous non-alkaline reaction, under conditions of their high concentrations,
or low-alkaline substances convert into more basic sub- and enter into interaction with clay minerals (Fig. 1) 20,
stances, for example, clay minerals into zeolites, hydromi- metakaolin 21, fly ash (Fig. 2) 22, granulated blast-furnace
cas into micas, etc., similar to the processes taking place un- slag (Fig. 3) 18, with the formation of water-resistant, alka-
der conditions of autoclave treatment – a low basic silicate line and alkaline-alkaline earth aluminosilicate hydration
hydrate is formed from lime-siliceous mixtures and trical- products that are similar to minerals of the zeolite and mi-
cium silicate hydrate is formed from a mixture of b-C 2S ca-types, along with calcium silicate hydrates.
326 Journal of Ceramic Science and Technology —P. Krivenko 2017

Fig. 1: Formation of various zeolites based on clays and sodium carbonate (a) and potassium carbonate (b) 20.

Fig. 2: AAC (source of aluminosilicate): metakaolin, fly ash 1, fly ash 2 vs. curing conditions and hydration products. An – analcime; A –
zeolite Na-A; P – zeolite P; R – zeolite R; HN – nepheline hydrate; HS – hydroxysodalite; Z – trona; T – sodium carbonate hydrate 22.
2017 Why Alkaline Activation – 60 Years of the Theory and Practice of Alkali-Activated Materials 327

Results of this study suggested that the basic composition state, as well as when necessary, with the introduction
of the AAC hydration products depending upon the type of alkaline oxides or alkali metal hydroxides from the
of the alkaline activator are: outside. As a result, hydration processes of high-ba-
I – (mixing liquid – water H 2O) – RO-SiO 2-H 2O; sic alkaline substances will be similar in their charac-
ter to natural processes of formation of stone-like sedi-
II – (alkaline activator as “mixing liquid” – alkali met-
ments of the feldspar and nepheline rocks, and in activ-
al hydroxides) – RO-SiO 2-H 2O, R 2O-Al 2O 3-
ity similar to OPCs. Hydration processes of low-ba-
SiO 2-H 2O, R 2O-RO-Al 2O 3-SiO 2-H 2O;
sic or alkali-free substances are similar in their charac-
III – (alkaline activator as “mixing liquid” – alkaline ter to natural processes of step-by-step conversion of
earth metal hydroxides) – RO-SiO 2-H 2O; pozzolana, lime-clay, lime-slag and slag (Portland) ce-
IV – (alkaline activator as “mixing liquid” – alkali car- ments;
bonates) – RO-SiO 2-H 2O, R 2O-Al 2O 3-SiO 2- • Hydrated high- and low-basic substances are similar
H 2O, R 2O-RO-Al 2O 3-SiO 2-H 2O; to natural mineral formations: water-resistant alumi-
nosilicate hydrates – to micas, zeolites and low-basic
V – (alkaline activator as “mixing liquid” – alkaline
calcium silicate hydrates, as well as to soluble hydrox-
earth metal carbonates) – RO-SiO 2-H 2O,
ides or silicates of sodium and potassium.
where: RO – CaO, SrO, BaO, MgO and R 2O – K 2O,
Na 2O, Li 2O. (3) Specific features of alkaline activation
Known in the art 23 is that processes revealing an ability
to hydrate by traditional aluminosilicate cements are at-
tributed to the possibility to transform the aluminum-sil-
icon-oxygen tetrahedra to a discrete state. Their hydrates
(sols) are capable of polycondensation with the formation
of gels – colloidal solutions and, finally, crystalline forma-
tions. The dissolution process is the breaking up of ion-
ic (Ca-O) and covalent (Si-O-Si, Al-O-Al and Al-O-Si)
bonds. The higher degree of ionicity of the bonds, the eas-
ier the substance is hydrated by water. In the case of Port-
land cement, this takes place at the expense of blocking a
discrete state of SiO 4 by a Ca-ion (for example, C 3S, C 2S).
In this state, due to protonization of the Ca-O bond, an
autocatalytic destruction of a mineral occurs when it is
mixed with water, with the formation of hydrated tetra-
Fig. 3: Compressive strengths of AAC vs type of alkaline activator hedra [SiO 4] 4- and [AlO 4] 5- as well as, according to 24,
and curing conditions 18 1 and 1’ – slag with Mb = 1.13 (Al 2O 3 = Ca(OH) +or Ca(H 2O)OH -.
6.75 %); 2 and 2’ – slag with Mb = 0.85 (Al 2O 3 = 15.85 %); 1 and When water is mixed with minerals having a low de-
2 – steam-cured specimens (t = 90 ± 5 °C; 3 + 7 + 2 h) 1’ and 2’ – gree of bond ionicity, such as CS, the ionic force of wa-
autoclave-cured specimens (t = 173 °C; 3 + 7 + 2 h).
ter (pH = 7) is not enough, because covalent bonds that re-
The studies led to the following conclusions: quire a different mechanism to break them prevail in the
• Physico-chemical processes taking place during hard- CS, for example, complexing while hydrating (similar to
ening of conventional calcium-based cementitious the conversion of SiO 2 into its hydrated forms). This is
building materials are similar to those of the chemi- achieved by changing the ionic force of the mixing medi-
cal weathering of rocks and formation of the structure um with the introduction of ions with good electron donor
of stone-like substances of sedimentary and metamor- properties, such as ions of alkali metals, which increase the
phous origin. These processes take place at different pH of the mixing medium 25, 26.
rates, since the starting materials vary in basicity and Just this idea was put forward in 1957 by
physical state; V. Glukhovsky 12, 18 when he proposed using com-
• Hydration processes in calcium-based cements, ow- pounds of alkali metals – the elements of the first
ing to a higher basicity and metastability of constituent group of the periodic table, such as, for example,
minerals, take place more actively compared to those Na(K) 2CO 3, Na(K)OH, N(K) 2O⋅nSiO 2⋅mH 2O. Based
of alkaline rocks of stable structure. Their hydration on in-depth analysis of mineral formation processes
products are water-resistant silicate and aluminate hy- taking place in nature and the role played by alkali
drates, as well as soluble hydroxide of calcium; metal compounds in these processes 18, a “kaolinite
• Acceleration of these processes both in natural rocks (OH) 4Al 2(Si 2O 5)+2NaOH” system was chosen as a
and artificial alkaline and alkaline-alkaline earth alumi- model system for the first stage.
nosilicates, which are similar in composition, in order The studies showed that under normal conditions, the
to reach upper limits under which they can be used in a process of synthesis of alkaline aluminosilicate com-
form of hydraulic cementitious materials, can be done pounds takes place very slowly over time, which is not
by converting a substance from a stable crystalline state compatible with process regimes in the production of
into a more active metastable state, including a glassy building materials. At the same time, it was concluded
328 Journal of Ceramic Science and Technology —P. Krivenko 2017

that the most widely found in nature are mixed alkaline-

alkaline earth aluminosilicate hydrates. All this allowed
the assumption that the elements of the second group of (4)
the periodic table (Ca 2+, Mg 2+, etc.) could be taken as
catalysts for the formation of zeolite-like compounds. This equation, according to Pfeiffer’s theory 27, 28, re-
The incorporation of alkali metal compounds in the ce- flects the amphoteric nature of aluminum. However, in
ment composition in much larger quantities than were compliance with the views on the polymeric nature of its
allowed, in compliance with the principles of composi- (aluminum) hydroxide, it is supplemented by the follow-
tional build-up of traditional cements based on calcium ing equation of reaction 23:
and magnesium compounds, suggested an assumption that
n[Al(H 2O) 3 (OH) 3] ↔ [Al(OH) 3] n + 3nH 2O. (5)
alkali metal compounds acted not only as activators of
Iron reveals its amorphous properties during conversion
hardening, but also as self-functioning components for
Fe 2+ → Fe 3+ and change of structural coordination from
the binding system Me 2O-MeO-Me 2O 3-SiO 2-H 2O, the
four-fold into six-fold coordination, which can be done in
main structure-forming products of which were low-basic
alkaline conditions.
calcium silicate hydrates and zeolite-like products. Low
Iron and aluminum hydroxides can act in the process of
basicity of the hydration products is attributed to specif-
coagulation structure formation both as cation and anion
ic features of the structure-forming processes taking place
constituents, thus promoting accelerated removal of hy-
in the case of the alkali-activated slag cements. Thus, hy- drosols into a solid phase and intensification of the pro-
drolytic destruction of the solid low-basic phase is caused cesses of hardening.
first of all by the breaking of the covalent bonds Si-O- The ≡Si-O - anions that occur in the breaking of the Si-
Si, Me 3+-O-Me 3+, Si-O-Me 3+ according to the following O-Si bonds are less capable of complexing compared to
scheme: hydroxylated atoms of silicon, thus retarding the process
of hydration. A negative charge of the oxygen atom pre-
(2) determines the increase of electron density in the silicon
atom due to more intensive q p-d p-interaction and results
in weakening of its electron acceptor properties. Further-
with the protonization of the Me 2+-O ionic bonds taking more, the ≡Si-O - anions can participate in a reverse reac-
place in parallel, as known to occur in highly basic sys- tion – polycondensation, thus decelerating breaking of the
tems 14, 17. Si-O-Si bonds.
At the initial stage of breaking of covalent bonds in the However, in the presence of cations of alkali metals (Me +)
alkaline medium with 9 < pH < 12, the OH – and Na + ions this does not happen, since these cations neutralize the
play a key role. However, according to views on the mech- ≡Si-O - anions. The occurrence of the ≡Si-O --Na + type
anism under which the Si-O-Si bonds break 26, with the in- bonds will impede a reverse reaction of the formation of
crease in degree of silicon atom surface hydroxylation up the siloxane bond; the ≡Si-O --anions are removed from
to 2…3 hydroxyl units, its electron donor-acceptor prop- the reaction and enter the colloid phase. Subsequently, the
erties tend to increase. This increases the probability of alkaline silicates that are formed can, evidently, enter into
participation of water molecules in the destruction of the cation-exchange reactions with ions of the alkaline earth
Si-O-Si bonds. In this case the probability of formation of (Me 2+) present in the solid phase, and, first of all, with the
the intermediate complex compounds, which decompose Ca 2+cations under the following scheme:
under the following scheme, is higher: ≡Si-O - + Na +↔≡Si-O-Na, (6)
and afterwards under the following scheme:
≡Si-O-Na+ OH -↔ =Si-O-Na-OH,
(7)
≡Si-O-Na-OH + Ca 2+→ ≡Si-O-Ca-OH + Na +.
(3)
In a similar way, the products of destruction with par-
ticipation of complex anions are: Al(OH) 4 -, Al(OH) 5 2-,
Al(OH) 6 3- as the aqua complexes ≡Si-O-Al-OH-Ca-OH
are removed.
Similar polarizing action is rendered by the OH –-ions Thus, an alkaline cation promoting the course of hy-
on the aluminosiloxane bond Al-O-Si. According to co- drolytic destruction of the low-active, low-basic phases
ordination theory 27, aluminates in an alkaline solution acts in the early stages of structure formation as a catalyst
are present in the form of complex anions: Al (OH) 4 -, Al of destruction. Later, as far as the condensation process-
(OH) 5 2-, Al (OH) 6 3-, the existence of which is dependent es proceed, it takes an active part as a co-partner of Ca 2+
on the pH of the mixing medium. Owing to amphoteri- and Mg 2+ in the structure formation processes. Thus it fa-
ty of polyvalent metals, the formation of gel of alumino- cilitates its modification due to formation of the alkaline
hydrate has specific features that depend on the pH of the and alkaline-alkaline earth aluminosilicate hydrates that
mixing medium. are morphologically homogeneous with low-basic calci-
In general, the reversible process of polycondensation um- magnesium silicate hydrate phases.
(destruction of the solid phase aluminate constituent) can It is important to note that the structural representative
be described, according to 28, by the following equation: of C-N-A-S-H gel in AACs (C-A-S-H[Na, 2H]) has the
2017 Why Alkaline Activation – 60 Years of the Theory and Practice of Alkali-Activated Materials 329

highest bulk modulus value, and this information, com- Table 1: Mineralogical composition of the cement hy-
bined with the formation energy and bond strength data dration products vs type of starting aluminosilicate con-
provide evidence that these alternative cements may be as stituent.
stable as the C-S-H gel in OPC paste. This is consistent
with a previous study that reported an increase in the bulk
modulus value as the Ca/Si ratio was lowered 29.

(4) Principles of compositional build-up of the alkali-

activated cements
Simulation of naturally occurring processes of conver-
sion of hydrated aluminosilicates into anhydrous ones al-
lowed the development of cementitious material systems.
Their hydration products are capable of changing their
chemical composition and crystal lattice from hydrous to
anhydrous, depending on the temperatures under which
the concretes will be in service.
As a result, an idea for creating cementitious materials
was transformed according to the following:
“OLD” scheme (Portland cement, high-alumina ce-
ment)

RO-SiO2 RO-SiO2 -H2 O
+ H2 O → (8) V. Glukhovsky proposed dividing cements into two types:
RO-Al2 O3 RO-Al2 O3 -H2 O
alkaline and alkaline-alkaline earth aluminosilicate hy-
“NEW” scheme (alkali-activated cement) drates 31. Later, they were divided into three types 32, 33:
 – high-calcium alkali-activated cements
Al2 O3 -SiO2
+ R2 O + H2 O – low-calcium alkali-activated cements
RO-Al2 O3 -SiO2 – hybrid alkali-activated cements
(9)
R2 O-Al2 O3 -SiO2 -H2 O (a) High-calcium alkali-activated cements
→
RO-R2 O-Al2 O3 -SiO2 -H2 O Alkali-activated Portland and alkali-activated slag ce-
where RO – Mg(Ca)O, R 2O(Na, K) 2O. ments can be representatives of this alkali-activated ce-
The following postulates have been laid down to describe ment model. Contents of SiO 2+CaO are over 70 mass%,
their formation 14, 18, 20: and content of Al 2O 3 is less than 20 mass%. The main re-
action product in this case is a C-S-H, which is formed at
• alkalis act not only as activators but as structure-form-
early stages of hydration. The alkaline N-A-S-H as well as
ing elements included in the formed phases as well;
C-N-A-S-H, as a result of the slower crystallization pro-
• phases of the hydration products being formed are
cess in these cements, occur at the later stages.
characteristic of the presence of R 2O-Al 2O 3-SiO 2-
Moreover, high pH-values of the medium in which the
H 2O and R 2O-CaO-Al 2O 3-SiO 2-H 2O as well as
hydration process takes place tend to block a transfer of
RO-SiO 2-H 2O;
the Ca-ions into solution, this is an explanation of the
• quantities of alkalis to be added are caused by the neces- absence of Ca(OH) 2 and the fact that the basicity of the
sity to meet a stoichiometric composition/stoichiom- resulting calcium silicate hydrate, as a rule, exceeds 1 34.
etry requirement of the alkaline and alkaline-alkaline R. Myers et al. 35 have developed a structural model to
earth aluminosilicate hydrates analogous to natural ze- describe these gels based on the constraints inherent in the
olites. cross-linked and non-cross-linked structures of different
A classification proposed by P. Krivenko 30 is based on tobermorite-like units (Fig. 4). This model enables a calcu-
the characteristic features of products of hydration and lation of the chain length, Al/Si ratio and degree of cross
hardening of the alkali-activated cements, the “edge” vari- linking for these more complex structures that cannot be
ants of which may be represented by the compounds of fully described by standard models for non-cross linked
two types, these are: alkaline aluminosilicate hydrates of tobermorite-like C-S-H gels.
the R 2O-Al 2O 3-SiO 2-H 2O system and alkaline earth Recent studies have also revealed 36 that it is possible that
metal silicate hydrates CaO-SiO 2-H 2O. some of the chemically bound Ca 2+ in C-A-S-H is re-
A variety of mixed alkaline-alkaline earth aluminosili- placed by Na +, leading to the formation of a C-(N)-A-S-
cate hydrates may fall within these ranges. Phase composi- H inner type gel in both NaOH-activated and silicate-ac-
tion of the hydration products of the AAC stone is deter- tivated slag cements C-(N)-A-S-H type gels. These have
mined by the starting constituent materials. On the basis also been observed in the interfacial transition zone be-
of a knowledge of these principles, the required properties tween siliceous aggregates and silicate-activated slag ce-
can be achieved by selection of appropriate starting con- ments 37, 38, having a lower Ca/Si ratio than is observed in
stituent materials (Table 1). the binding gel formed in the bulk region.
330 Journal of Ceramic Science and Technology —P. Krivenko 2017

(b) Low-calcium alkali-activated cements. In an initial attempt at determining the compatibility of

The representatives of this alkali-activated cement mod- [N-A-S-H]-[C-A-S-H] gels, the possibility of co-precip-
el are the alkali-activated cements in which clays or type F itating the two cementitious gels in a sol-gel process was
ashes with low CaO content are used as an aluminosilicate studied 46, 47. The laboratory reagents were a sodium sili-
raw material. The model of the structure formation pro- cate (source of silicon), calcium nitrate (source of calcium)
cess was described by V. Glukhovsky 18 and further devel- and aluminum nitrate (source of aluminum) solutions. The
oped in other works 14, 20 – 22, 33, 39 – 41. The main reaction alkalinity of the medium was controlled with a NaOH so-
product formed in this case is a three-dimensional, inor- lution. The synthesis parameters analyzed were pH and
ganic alkaline polymer N-A-S-H or “geopolymer”, which the initial Si/Al and Ca/Si ratios. The resulting synthetic
can be regarded as a zeolite precursor (Fig. 3) 31. gels were characterized with XRD, TEM/EDX and NMR.
The structure of the gels forming in the alkaline activa- The findings showed that the type of products formed and
tion of low-calcium aluminosilicate materials differs sub- their characteristics depended heavily on the pH in the
stantially from the structure of the gels formed in the ac- synthesis medium and the initial Ca/Si and Si/Al ratios.
tivation of calcium-rich cements. These (N-A-S-H) gels While a medium-high lime content favored the formation
are characterized by a three-dimensional (3D) structure in of C-A-S-H gels, the presence of a high alumina and silica
which the Si is found in a variety of environments, with a content led to the formation of an N-C-A-S-H gel.
predominance of (Q 4) and (nAl) (n = 0, 1, 2, 3 or 4) units Very recently, the same group of authors 48 proposed a
(Fig. 5) 42, 43. tentative phase diagram for the Na 2O-CaO-AI 2O 3-SiO 2
(c) Intermediate calcium alkali-activated cements – hy- system at 25 °C, based on a series of solution/precipita-
brid cements tion studies. At pH values relevant to cement, the predom-
inant phase was a solid solution designated C-A-S-H with
The compositional build-up of the hybrid alkali-activat-
compositional ranges of 0.72 < CaO/SiO 2 < 1.94 and 0 <
ed cements often requires the use of starting constituent
materials with various contents of Ca +2 and Al +3, such as Al 2O 3 /SiO 2 < 0.1. The Na 2O content in this and related
for example, OPC+slag (ggbs)+fly ash, slag (ggbs)+kaolin CaO-rich phases was negligible, all phases being assumed
(metakaolin) OPC+fly ash, slag (ggbs)+fly ash, slag (gg- to be water-saturated.
bs)+red mud, etc. Contents of Al 2O 3 in these cements are A gel denominated N-A-S-H, exhibiting a three-dimen-
higher than 20 % 44, 45. sional structure, was also observed in this system. In the
The reaction products precipitating as a result of hybrid presence of Ca, however, it was only found to be stable at
cement hydration are very complex and comprise a mix of low pH values (< 12). At high values (> 12), the presence
cementitious gels, including C-A-S-H (containing sodi- of Ca favored C-A-S-H formation to the detriment of N-
um) and (N, C)-A-S-H (high-calcium-content N-A-S-H A-S-H. At low pH, this phase behaved like a zeolite and
gels) ones. The following is a description of the most sig- an ion exchange process was observed in which the Na +
nificant features of the aforementioned procedures and the was replaced by Ca 2+ until the stone of the latter was com-
activation reactions governing each. pletely depleted.

Fig. 4: Schematic representation showing cross-linked and non-cross-linked tobermorite structures that represent the generalized structure of
the C-(N)-A-S-H type gel 35.

Fig. 5: Model proposed for the N-A-S-H gel formation 48.

2017 Why Alkaline Activation – 60 Years of the Theory and Practice of Alkali-Activated Materials 331

A study was conducted on the compatibility between ce- oxides in the Me 2O-MeO-Me 2O 3-SiO 2 system, and con-
mentitious gels by directly mixing pre-synthesized C-S-H ditions under which the synthesis takes place. At the first
or C-A-S-H with N-A-S-H 48. Based on the observation stage, the alkaline cations Me + act as a catalyst of destruc-
that the two gels inter-reacted under these conditions, it tion of the Si-O-Si, AlO-Al and Si-O-Al bonds. At the
was predicted N-A-S-H would gradually degrade to C- second stage, they participate as co-partners of the cations
A-S-H until the C-A-S-H reached a composition reflect- Me 2+ in the formation of the alkaline or alkaline-alkaline
ing its minimum CaO/SiO 2 and maximum Al 2O 3/SiO 2 earth aluminosilicate hydrates similar to natural zeolites.
ratios. In the resulting mixture, the remaining N-A-S-H
and C-A-S-H gels would be in equilibrium. Acknowledgement
These hybrid materials can be divided into two groups. The author would like to express his sincere gratitude to
Group A includes materials having a low Portland ce- Professor Waltraud M. Kriven from the University of Illi-
ment clinker content and a high proportion (over 70 %) nois at Urbana-Champaign, USA, for her great contribu-
of mineral additions. Examples are: OPC+slag (ggbs), tion to research on alkali-activated materials and for pro-
OPC+fly ash, OPC+slag (ggbs)+fly ash 49 – 53. Group moting this publication.
B comprises blends without Portland cement: slag (gg-
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