J. Am. Ceram. Soc.
, 91 [12] 3864–3869 (2008)
Journal
Designing Precursors for Geopolymer Cements
Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010, Australia
This paper presents a discussion of the ability to design raw
materials for use in geopolymers. To provide a ‘‘green’’ material
to complement existing cement binders, as well as in the interests
of waste beneficiation, various potential means of tailoring geo-
polymer precursor chemistry and particle behavior are outlined.
The opportunities presented by the development of one-part
‘‘just add water’’ geopolymer formulations are identified as
exceeding the potential of the traditional two-part (solid plus
alkaline activator solution) mix design. The key roles played
by network-modifying (alkali and alkaline earth) cations and
alumina in rendering glassy phases ‘‘ideal’’ for geopolymeriza-
tion are discussed, and the potential value of ASTM Class C
ashes in synthesis of high-performance geopolymers becomes
evident. This provides a significant step toward the development
of international standards for the application of geopolymer
binders in the construction industry worldwide, and raises a
number of important challenges for researchers in the field of
geopolymer and cement technology.
I. Introduction
I T is well known that the cement manufacturing industry is one
of the most energy intensive of man’s activities.1 However,
cement is also the basis of most modern construction through its
use in concrete. Thus, the cement and concrete industries are
under increasing pressure not only to improve energy efficiency,
but also to find acceptable quantities of raw materials for the
manufacture of cement clinker. Improvements in energy effi-
ciency have done much to reduce the impact of cement on the
environment, but the massive increase in cement demand from
the developing world is fast outpacing efficiency gains. Supplies
of lime, sand, and aggregates are limited, and there is a need for
new cement products, compatible with ordinary Portland ce-
ment (OPC), to create new solutions to upcoming problems.
Therefore, raw materials which can be readily found in all areas
of the Earth’s crust, or in widely available waste streams, must
be investigated.
‘‘Geopolymer’’ is the generic name given to alkali-activated
products derived from aluminosilicate-bearing raw materials.2
Davidovits3 coined the term several decades ago, but the initial
detailed research into these materials was conducted in Ukraine
during the 1950’s.4,5 This paper explores different raw materials
used in geopolymer manufacture. The primary aim of the dis-
cussion is to understand what makes a ‘‘good’’ raw material for
generic two-part (solid source plus alkaline activator) geopoly-
mer synthesis, and with that in mind move toward the design of
a successful one-part ‘‘just add water’’ geopolymer formulation
capable of competing on an equal footing with Portland cement
technology. In order to do this, an analysis of the traditional
two-part geopolymer processes, raw materials and paths to
L. Klein—contributing editor
Manuscript No. 24714. Received May 22, 2008; approved September 15, 2008.
This work has been financially supported by the Australian Research Council (ARC),
including partial funding via the Particulate Fluids Processing Centre, a Special Research
Centre of the ARC.
w
Author to whom correspondence should be addressed. e-mail: jprovis@unimelb.edu.au
3864
DOI: 10.1111/j.1551-2916.2008.02787.x
r 2008 The American Ceramic Society
Peter Duxson and John L. Provisw
optimal properties that can be derived by manipulation and
combination of raw material feedstocks is conducted.
II. Raw Materials for Two-Part Geopolymers
The three most common raw material classes used in geopoly-
merization are slags, calcined clays, and coal fly ashes. Each of
these has been widely studied as a supplementary cementitious
material in Portland cement-based systems, and the reader is
referred to the cement literature for a detailed discussion of their
performance and properties in that context. Calcined clays (pre-
dominantly metakaolin) have been relatively widely used in geo-
polymer synthesis, but due to their plate-like particle shape tend
to lead to an unfeasibly high water demand and high porosity in
concrete applications. While valuable for scientific investigation
purposes, this high water demand means that calcined clays will
not be considered in detail in this paper. Other types of raw
materials have been used for two-part geopolymer synthesis, in-
cluding in particular synthetic powder precursors6,7; however,
their use is not yet widespread.
(1) Metallurgical Slags
While there are many types of slag that may be activated by
alkaline solutions,8,9 this article focuses on ground granulated
blast furnace slag (GGBFS), a by-product of iron manufacture,
as it is the most common and widely known to the cement and
concrete industry. As slag is generated in the blast furnace and
subsequently quenched, its composition is essentially that of an
over-charge-balanced calcium aluminosilicate framework (i.e.,
there is more than sufficient calcium available to charge-balance
aluminum, with the remainder contributing to depolymerizing
the glass network).10 In geopolymers, the key network forming
cations are Al31 and Si41. The divalent cations Ca21 and Mg21
act as network modifiers, providing the charge balance required
by tetrahedral aluminum as well as any depolymerized frame-
work sites.
Critically in the context of geopolymer manufacture, as well
as in its wider use as a supplementary cementitious material for
Portland cement concrete production, GGBFS from a particu-
lar blast furnace is reasonably consistent in chemical and phys-
ical properties. This is mainly due to two factors: (1) monitoring
of slag composition and properties is often used for quality
control in iron production,11 meaning that a well-run blast fur-
nace will produce a very consistent slag; and (2) GGBFS par-
ticles are generally homogeneous, being formed by comminution
of larger glass particles. However, despite this quality control
within individual locations, slag compositions do vary between
specific furnaces and ores. The reactivity of different slags in
alkali-activated materials in terms of composition, glass struc-
ture, origin, water demand, workability, shrinkage, and particle
size is relatively well understood as a result of the work of Shi
et al.5 and others. Figure 1 shows a typical SEM image of a slag.
There are a variety of different formulae used worldwide for
calculating slag reactivity,5 and a new equation incorporating
the importance of phase separation in glasses in determining
reactivity is presented here. In terms of the strength development
characteristics of alkali-activated materials, the precursor oxide
composition can be used to calculate the expected reactivity.
December 2008 Precursors for Geopolymer Cements
100 µm
Fig. 1. SEM image of a typical ground granulated blast furnace slag,
showing the irregular morphology but relative chemical homogeneity of
the slag glass particles. Reprinted from reference Wan et al.12 with per-
mission from Elsevier.
GGBFS is broadly described as a mixture of phases with
compositions resembling gehlenite (2CaO
Al2O3
SiO2) and
akermanite (2CaO
MgO
2SiO2), as well as a depolymerized
calcium silicate glass. The degree of depolymerization (DP)
largely controls reactivity. Gehlenite and akermanite are as-
sumed here to form stoichiometrically—although potentially in
glassy rather than crystalline form, depending on cooling rate—
and the remaining elements form a highly reactive depolymer-
ized glass. There is also some sulfur present, which is assumed to
bind 1 mole of Ca per mole of S. The degree of DP of the glass
network is then defined as the molar ratio of free Ca to free Si
Total Ca  Ca in gehlenite  Ca in akermanite
Free Ca Ca associated with S
¼ widely. However, there are trends that can be identified by com-
Free Si Total Si  Si in gehlenite  Si in akermanite
(1)
Assuming that all the Mg present is in akermanite and all the
Al in gehlenite, the quantities of Ca and Si in these phases can be
calculated, with the Mg and Al concentrations substituted into
Eq. (1) to give Eq. (2)
nðCaOÞ  2nðMgOÞ  nðAl2 O3 Þ  nðSO3 Þ
DP ¼
nðSiO2 Þ  2nðMgOÞ  0:5nðAl2 O3 Þ
This ratio is typically in the range of 1.3–1.5 for GGBFS, with
higher values indicating a more depolymerized and therefore,
more reactive silicate network. While this expression does not
account for differences in reactivity due to different slag glass
quenching procedures, it provides at least an estimate of intrin-
sic potential for reactivity.
It is also observed in the literature that the reactions of slag
are dominated by small particles. Particles 420 mm in size react
slowly, while particles o2 mm react completely within ap-
proximately 24 h in blended cements and in alkali-activated
systems.12,13 Clearly, when using slag in geopolymerization, care-
ful control of particle size distribution can be utilized to control
the strength development profile, as is done in OPC blends.12
(2) Fly Ash
The spherical particle shape of fly ash, seen in Fig. 2, is beneficial
for reducing water demand and for maximizing particle packing
to reduce porosity. Fly ash consists of the remnants of clays,
sand, and organic matter present in coal, which leave via the
chimney of the furnace during combustion. These compounds
are melted in the furnace, but are then quenched rapidly in air to
produce small, generally spherical glass particles. However,
3865
5 µm
Fig. 2. SEM image of a Class F fly ash, obtained from Gladstone
power station, Australia, showing polydisperse and predominantly
spherical particles.17
crystalline phases are also present, and heterogeneity is observed
on both interparticle and intraparticle levels.14–16 Therefore, fly
ash is a highly variable material that is dependent not only on
the impurities present in the coal before combustion, but also on
the particulars of the combustion and the quenching process.
The fly ashes that are most widely used in geopolymer synthesis
are low in Ca, i.e., Class F according to ASTM C618. Published
work on higher Ca (Class C) ashes is scarcer, possibly due to the
rapidity with which setting may occur in systems of ‘‘standard’’
geopolymer design. As such, these two classes of fly ash will be
dealt with separately here.
(A) Class F ash: The reactivities of fly ashes, and the
nature of the geopolymeric products produced from them, vary
parison of the ash composition and geopolymer strength data,
as shown in Fig. 3. This plot shows the overall oxide composi-
tions of a number of ashes, as well as an indication of the
strength achievable by activation of those ashes. Given that the
data are sourced from a number of publications where samples
were formulated and cured very differently, the exact strength
data are not directly comparable; however, categorization as
‘‘high,’’ ‘‘medium,’’ or ‘‘low’’ provides some useful insight. The
multicomponent compositional data are converted to pseudo-
ternary data by combining the alkaline earth (M21O) and alkali
(2) metal (M1
2 O) oxides, representing these components by the sum
SiO2
Mol %
High strength
Medium strength
20 80 Low strength
GGBFS
40 60
60 40
80 20
Mol %
1/ Al O
2 2 3 2 M2+ O+1/2M+2O
20 40 60 80
Mol %
Fig. 3. Pseudo-ternary composition diagram for fly ashes, showing
ashes leading to alkali activation products in approximate strength
ranges as shown. Alkali and alkali earth oxides are summed, and rep-
resented as the total number of charges on the respective cations. Com-
position and strength data compiled from references van Jaarsveld and
colleagues18–20 as well as previously unpublished data. For comparison,
compositions of a selection of blast furnace slags5 are also shown.
3866 Journal of the American Ceramic Society—Duxson and Provis
of the charges on all network-modifying cations—so an alkali
metal cation counts as one charge unit, and an alkaline earth
cation as two. Iron, titanium, unburnt carbon, and other ele-
ments present are not included in this analysis, and the compo-
sitions are normalized to account for this.
From Fig. 3, it is clear that ashes with low network modifier
content tend to produce poor alkali activation products, with
strength generally increasing as a function of network modifier
content for Class F ashes. The only ash depicted that is not
Class F is the rightmost of the black points shown; this is a
Class C ash, and its alkali activation gives products of high
strength.19 Figure 3 also shows the compositions of some rep-
resentative blast furnace slags, which are very high in Ca and
low in Al compared with fly ashes.5 The distinction in Fig. 3
between the ‘‘medium’’ and ‘‘high’’ categories is not completely
clear-cut on purely compositional grounds; however, it is ob-
served that high-strength geopolymers are in general derived
from ashes in the higher alumina part of the compositional re-
gion shared by these two categories. Another (related) point of
note is that the only ‘‘low-strength’’ ash with a significant net-
work modifier content (sourced from Mount Piper, Australia) is
also close to the lowest in Al2O3 of all the ashes depicted.
It is also notable that Hemmings and Berry14 developed a
correlation between total network modifier content and the
2ymax value of the broad X-ray diffraction (XRD) peak as-
signed to the glassy phases present. While a similar analysis has
not been carried out for the compilation of ashes presented in
Fig. 3, this may be of value in the analysis of ash reactivity for
geopolymerization.
(B) Class C Fly Ash: The observation that network
modifier content is an indicator of the potential utility of a
given fly ash in geopolymerization will obviously bring attention
to the use of Class C fly ashes. This class of ashes has not been
subjected to the same level of analysis in the literature as have
Class F ashes, with only a handful of publications to date.19,21–24
Roy et al.24 and Lukey et al.25 have shown that not only is it
possible to utilize Class C fly ash in geopolymers, but in fact it
can be largely preferable if the rheology of the mix can be ad-
equately controlled. From a compositional viewpoint, the only
significant difference between Classes C and F ashes is the cal-
cium content, as the division between the two classes is largely
arbitrary. Indeed, Class C fly ash could be viewed (within rea-
son) as compositionally in between Class F fly ash and GGBFS.
The fact that GGBFS-Class F ash mixes are often preferred in
the production of geopolymers also provides an indication of
the potential of Class C ashes. However, if there exists an op-
timal precursor composition for geopolymer formation, then it
is clear that a better understanding of the role of glass chemistry
in fly ash is required, not least because Class C fly ash is less
abundant than Class F ash.
(C) Fly Ashes and Glass Chemistry: Unlike the more
homogeneous glassy phases in GGBFS, fly ash contains a myr-
iad of different phases, with both interparticle and intraparticle
inhomogeneity observed widely.14 Despite this complexity,
much information is available in the literature detailing the na-
ture and reactivity of the phases present in fly ashes in terms of
both their chemical and physical availability.17,26,27 Analysis of
the kinetics of fly ash geopolymerization is complicated some-
what by the heterogeneity of the system. However, major
advances have recently been made by the use of infrared spec-
troscopy, which enables in situ analysis of the reaction
process.28,29
It is clear that the exact details of the geopolymerization pro-
cess depend on the individual ash source selected, and that no
two ashes will follow exactly the same mechanism. Detailed
analysis must therefore be based on an understanding of how
each phase observed in fly ashes reacts under geopolymerization
conditions. Knowledge of which phases are present—and,
critically, which are accessible during geopolymerization as op-
posed to being encapsulated by a shell of unreactive material26—
will then enable the correct mechanistic analysis to be applied to
each specific ash source. This is by no means a trivial task, as it
Vol. 91, No. 12
necessitates the development of a database of the chemistry, re-
activity, leaching rates, and dissolution mechanisms of all the
different glasses observed in fly ashes, and then a detailed min-
eralogical and crystallographic analysis of every batch of ash to
be processed. Some preliminary work has been completed
involving linking the concepts and techniques developed by
Hemmings and Berry14 with geopolymer chemistry19 and in
modeling of ash dissolution.26 However, the laborious nature of
this work necessitates a more technologically and intellectually
accessible approach, as will be outlined below.
III. Availability of Aluminum
It is well known that the availability of aluminum controls to a
large degree the properties of geopolymers.2,27,30 The absolute
amount of available aluminum and the rate of its release
throughout reaction not only affect final strength, but other
properties in the wet and hardened states including setting char-
acteristics, flexural strength, acid resistance, microstructure, and
strength development profile. The availability of silicon is also
important, but ultimately less critical as any deficiencies in the
solid source can be accounted for by direct addition via the ac-
tivating solution. Therefore, by understanding the nature and
rates of the dissolution of aluminum from a precursor, it
becomes possible to predict and control the properties of the
resultant geopolymer.
Only a small change in aluminum incorporation rates is ob-
served when activating metakaolin with alkaline solutions con-
taining different alkali metals, indicating that the aluminum in
metakaolin is readily available.31 In contrast, the release of alu-
minum from fly ash is considerably slower, and is greatly
affected by alkali concentration and type.17,20,32 This indicates
that the availability of aluminum from the glassy phases in fly
ash is limited by the nature of those phases, regardless of the
crystallinity of the remainder of the ash.
Thermodynamic calculations33,34 and sorption/speciation
arguments34,35 show that most Al(IV)–O–Si bonds are more
readily broken than Si–O–Si bonds, and bonds between net-
work-forming and network-modifying species are weaker yet.36
Once network-modifying cations are introduced into alumino-
silicate glasses above the level required for charge-balancing of
tetrahedral aluminum, these associate predominantly with sili-
con due to the greater tendency of tetrahedral silicate sites to
host nonbridging oxygen (NBO) atoms.37 The glassy phases
most likely to provide aluminum during geopolymerization are
these depolymerized glasses. Conversely, if there is insufficient
network-modifying charge available to fully coordinate with
aluminum, then the solubility of the aluminum from that phase
is greatly reduced as it tends to take on 6-coordination. Divalent
alkaline earth cations enhance dissolution compared with
monovalent alkali cations, enabling glasses to show different
dissolution rates according to composition.
Figure 4 provides an illustration of the dissolution mecha-
nism of a glass containing both monovalent and divalent net-
work-modifying cations. The illustration follows in a general
sense from the arguments of Oelkers et al.38 and of Hamilton
et al.34 although does not reproduce in detail the mechanisms
outlined by those authors. The primary distinction between the
Na1 and Ca21 sites shown is the much greater extent of ‘‘dam-
age’’ caused to the glass structure by the removal of a divalent
cation than a monovalent one. It has been proposed that the first
step of the mechanism of glass dissolution at moderately high
pH resembles that observed under acidic conditions, being ini-
tiated by ion exchange of H1 for Na1 or Ca21.39 While it is
difficult to conceive that such a mechanism is significant at a pH
approaching 14, as is the case in the initial stage of two-part
(alkali-activated) geopolymer syntheses, it will definitely be pos-
sible early in the reaction of a one-part geopolymer mix.
While it is well known that the network breakdown process
during glass dissolution is largely controlled by surface-charging
behavior,40 the exact mechanistic details of this process (even for
December 2008 Precursors for Geopolymer Cements 3867

(a) H O (b) polymerization by utilizing quantitative XRD in combination

H O H O with compositional analysis and devitrification to determine the
H O H O Ca chemistry and compositions of the reactive phases. However, in
O Si O Si H O practical terms, the supply of ‘‘good’’ ashes is often both limited
O H+ O
O O H O in gross volume and geographically isolated from major con-
Si Si
H+ H O crete markets. The only way to run a concrete batching oper-
Si O– O Si O– O– ation cost effectively is to utilize as far as possible locally
H+ available bulk materials. Based on experience, there is a high
Al Al H O
Ca H O
O– O– likelihood that of the local materials at a given location, few if
O O any will have highly favorable glass chemistry, and even if one
Si Si does, it is likely to be in high demand (either by OPC concrete or
Si H O Si
O O OH – rival geopolymer manufacturers). Therefore, it is critical that
O– O– alternative ashes need to be used if a true geopolymer industry is
Al H+ Al H O to be created, and possibly that poor ashes may be somehow
Na+ H+ Na+
upgraded to a higher quality at extremely low cost. GGBFS
pH ~ 7–10 pH ~ 11–12
provides an obvious source of highly reactive glass, but is priced
similarly to OPC in many markets and so drives up cost.
(c) (d)
H O H O
H O
Clearly, the key is to optimize reactive glass content while keep-
H O
OH – Ca OH Ca ing price and performance within commercial parameters.
H O O Si H O This real-world trade-off introduces the concept of a product
O Si O
O ‘‘sweet spot,’’ where price, reactivity, water demand, and
H O O OH
O OH Si
Si strength characteristics are optimized. This will be different for
H O Si
Si O–
O– H O every geographic location, taking into account the properties
OH Al(OH) – and costs of the available raw materials. So, in terms of a real-
Al H O world geopolymer industry, there is no such thing as an optimal
O H O H O OH
O– O–
geopolymer composition, but rather a collection of possible mix
Si designs utilizing a broad variety of raw materials that achieve
Si
Si(OH) O –
O
Si O a balance of commercial and technical goals. As raw material
O···Na OH Na+ availability, quality or price change, a producer must be able to
OH
Al
Al H O react quickly to compensate in a timely and cost-competitive
H O
manner. The intellectual complexity of this process is clear from
pH ~ 11–12 pH ~ 11–12 the discussion above, and is not conducive to large-scale com-
mercial implementation. For a true geopolymer industry to
Fig. 4. Dissolution mechanism of an aluminosilicate glass during the develop, a simple and effective method must be formulated.
early stages of reaction of a one-part geopolymer mix. (a) Exchange of
H1 for Ca21 and Na1, (b) hydrolysis of Al–O–Si bonds, (c) breakdown
of the depolymerized glass network, and (d) release of Si and Al.
Charged framework oxygen sites are marked in bold; note the charge V. Designing One-Part Geopolymer Cements
transfer reaction occurring between panels (b) and (c), and proton trans-
fer throughout. All framework Si and Al sites are tetrahedrally coordi- OPC is formed by the very deliberate manufacture of a reactive,
nated to oxygen, but additional bonds are not shown for clarity. predominantly calcium silicate material, containing the correct
constituents and phases to provide nutrients for reactions at a
more straightforward situations such as crystalline quartz dis- given rate in the presence of water. The dissolution behavior of
solution) remain the subject of much discussion.41 It is not the OPC is determined predominantly by chemical composition and
purpose of this paper to investigate these issues on an atomistic particle fineness, and has been refined over a long period of time.
level, although that will clearly be required if the mechanism of Calcium is present in sufficient quantities to depolymerize the
geopolymerization is to be fully understood. Hence, Fig. 4(b) silicon, giving rapid initial dissolution when compared with a
shows attack by both water and hydroxide on the particle,42 but slag or a fly ash under the same conditions of near-neutral initial
the exact locations at which each process will occur are not pH. As the pH increases during OPC hydration, any slag and/or
specified. Similarly, some glasses show synchronous release of Si ash present will begin to react. This is why these components are
and Al while others leach one component preferentially—this is known to be beneficial primarily in development of later-term
strongly dependent on the specific glass used and also the leach- properties of a blended cement; they simply do not react rapidly
ing environment, and the specific details are well beyond the enough at a pH of 10–11 to contribute significantly to the initial
scope of this paper. period of cement hydration. In terms of the discussion in the
The presence of alkaline earth cations in a glass also gives an preceding section, OPC presents itself as the ‘‘sweet spot’’ com-
increased tendency toward framework disorder, including the position for calcium silicate chemistry, and perhaps a similar
formation of a small concentration of (weak, reactive) Al–O–Al approach can be used for manufacturing a one-part ‘‘just add
bonds, as well as an NBO content higher than is strictly required water’’ aluminosilicate-based geopolymer cement.
by stoichiometry.37,43 For these reasons, it is easy to understand Existing one-part geopolymer mixes generally involve the use
how slag, rich in Ca21 and Mg21 as modifiers, provides an ex- of very finely ground solid precursors, which give a high extent
cellent raw material for alkali activation. This fundamental glass of reaction very rapidly but with as yet limited control over
theory is supported by the observed differing reactivity of kinetics, a relatively high water demand and problematic
GGBFS and a variety of different Class C and Class F fly rheology.44 There are many conceivable routes for manufactur-
ashes. An optimal glassy phase, or combination of glassy phases, ing highly favorable glasses for geopolymerization. Three pos-
would allow the tailored control of geopolymerization, includ- sibilities, each based around the concept of providing the right
ing workability, setting time, strength development profile, and balance of components at each stage of the geopolymer cement
durability. production process, are presented here:
Route (1): Addition of components into pulverized coal be-
fore combustion to artificially manufacture an ash of pre-
dominantly known and desired glass composition. Potential
IV. An Optimal Two-Part Geopolymer?
additives can be identified by analysis of the reactive phases
Following the work of Hemmings and Berry14 as well as the in existing ashes by devitrification techniques. For example,
discussion above, it is possible to identify a ‘‘good’’ ash for geo- glass phases including calcium-containing feldspars such as
3868 Journal of the American Ceramic Society—Duxson and Provis
labradorite and anorthite may be targeted. It is necessary that
enough calcium finds its way into the glass phase of the resultant
ash to make it highly reactive, as well as the need to add enough
alkali-containing phases to balance the aluminum present. How-
ever, this method requires altering the finely balanced conditions
used for coal combustion, which is hard to achieve on a com-
mercial level at this time.
Route (2): Manufacture the favorable glasses that are respon-
sible for the good qualities of fly ashes by melting the above-
mentioned materials separately, to create a clinker similar to
cement, but based on alkali aluminosilicate chemistry as op-
posed to calcium silicate chemistry and hence giving lower CO2
emissions.45 This clinker must then be ground to a particular
fineness. This has a disadvantage compared with Route (1) in
that the particles have an irregular shape, which will increase
water demand compared with fly ash, but does not interfere with
the coal combustion process. Additionally, as this process is in-
dependent of the initial ash generation, a production facility
could manufacture the highly reactive phases and blend them to
add value to otherwise poor-quality ashes.
Route (3): Preparation of an ideal glass by utilizing geopoly-
mer as a reaction intermediate. Routes (1) and (2) have the
drawbacks of not producing a glass that can react with water to
produce a one-part geopolymer mix. By combining different raw
materials, as described above, to generate a two-part geopoly-
mer mix with optimal properties, one can generate a glass pre-
cursor of ideal composition. This material may be clinkered in a
rotary kiln to produce a genuine one-part geopolymer precur-
sor, which can be utilized directly or blended with ash and/or
slag.
Routes (1) and (2) provide a means for production of value-
added raw materials most predominantly for conventional
two-part geopolymer processes, while route (3) provides for
the production of a one-part geopolymer glass. The addition
of sufficient alkali to the glass in a safe and cost-efficient manner
is the main barrier to the success of this process. The idea of
intimately combining of two or more components to manufac-
ture a highly reactive glass is not necessarily new, but its im-
portance has not been widely recognized in the field of
geopolymer chemistry. Kriven et al.46 have utilized the geopoly-
mer process to manufacture highly compositionally controlled
precursors for further processing at high temperature, while
Duxson et al.47,48 noted the ability of geopolymers to form
glasses at relatively low temperatures over wide compositional
windows. Route (3) takes this process in a slightly different di-
rection to enable low-cost glass manufacture, and utilizes widely
available cement production equipment such as rotary kilns and
grinding circuits. A technology called ‘‘Sialite’’ is based on sim-
ilar principles, and has recently been commercialized in China.49
The fineness of cement is routinely used to control reactivity,
by means of milling. However, this has the deleterious effect of
increasing water demand due to the irregular shapes of particles
subjected to intense comminution.12 Water demand depends
strongly on the surface area of the solid precursor, meaning that
fine, irregular particles require the addition of much more water
to the mix for a workable binder to be obtained. Spherical fly
ash glass particles will in general have a low water demand as
spheres have the lowest surface area per unit volume. Low en-
ergy, short-duration milling of fly ashes for use in blended ce-
ments does in fact decrease the water demand of the ash, by
breaking down irregular particle agglomerates and plerospheres
(hollow particles filled with smaller spheres), without affecting
the morphology of the majority of the other particles.50,51 How-
ever, high-energy milling of the type required for significant
particle-size reduction causes fracture of many classes of parti-
cles, leading to the observed increase in water demand.
Water reduction is desirable in terms of many of the proper-
ties of concretes, as well as from an environmental perspective.
In particular, low water/binder ratios give reduced permeability,
meaning that corrosion of steel reinforcing due to chloride or
sulfate attack is greatly reduced, and the lifespan of the concrete
is able to increase markedly. The design of a one-part geopoly-
Vol. 91, No. 12
mer precursor should take this into account also, meaning that
fine spherical particles are preferred over larger particles milled
to a smaller size but irregular shapes. This may be possible uti-
lizing new fluidized bed reactors, but would not take advantage
of the opportunity to utilize existing cement kilns.
VI. Geopolymers and the Future Cement Industry
Geopolymers are not necessarily a product competing with
OPC, but rather a technology, which may be utilized by cement
producers to offer a broader range of cementitious products to
the market. Clearly a one-part process is the ideal mechanism
for large-scale deployment of geopolymer cements, as most of
the quality control processes can be dealt with centrally. This is
not to say that this proposition is currently feasible or close to
market readiness. In contrast, two-part geopolymer concrete
production is ready for commercialization, subject to sufficient
quality control and access to appropriate technology to either
cope with or remove the need for regular mix-design adjust-
ments. Such an operation has commenced medium-scale
production in Australia early in 2008.52
To achieve broad-based market penetration, a geopolymer
concrete needs to be low cost, environmentally beneficial
(‘‘green’’), should make use of existing concrete infrastructure,
and not cause notable Occupational Health and Safety con-
cerns. On a practical and operational level, this translates into
high ash/slag ratio systems, low (or no) free alkali, a one-part
mix, and the ability to utilize as much current cement processing
practice as possible. Each of these aspects can be covered by
the introduction of appropriate geopolymer technology, as
discussed above.
VII. Conclusions
If it were possible to have a choice of ideal raw materials for
geopolymerization, it would be important to be able to control
the dissolution rates of the glassy phases present. This can be
achieved by optimization of the addition of readily available
network-breaking cations (Ca21, Mg21, Na1, K1) during pre-
cursor synthesis. By the use of standard glass synthesis meth-
odology, it should be entirely possible to generate a glass of the
necessary composition (including network-breakers and net-
work-modifiers) to enable synthesis of geopolymers by ‘‘just
adding water.’’
By synthesizing the precursor as spherical glass particles, it
will be possible to retain the benefits of spherical particle shape
observed in fly ash. The need for addition of alkali may be either
greatly reduced or even eliminated if the correct glass, or a com-
bination of glasses, can be selectively synthesized. It is possible
that this may be achieved by addition of components in to pul-
verized coal, or by the selective manufacture of a highly reactive
raw material that can be blended with less-reactive raw materials
to provide a geopolymer cement to a given specification.
This paper, therefore, poses the challenge to workers in the
field: There is a clear need for a workable one-part mix design if
geopolymeric cements and concretes are to achieve widespread
market penetration. A methodology for designing the necessary
precursors has been proposed, but its successful large-scale
implementation has not yet been demonstrated.
Acknowledgment
We thank Professor Jannie van Deventer for his unstinting support and guid-
ance during the development of this paper.
References
1
K. Humphreys and M. Mahasenan, ‘‘Toward a Sustainable Cement Industry.
Substudy 8: Climate Change,’’ World Business Council for Sustainable Develop-
ment, 2002, 92pp.
2
P. Duxson, A. Fernández-Jiménez, J. L. Provis, G. C. Lukey, A. Palomo, and
J. S. J. Deventer, ‘‘Geopolymer Technology: The Current State of the Art,’’ J.
Mater. Sci., 42 [9] 2917–33 (2007).
December 2008 Precursors for Geopolymer Cements
3 28
J. Davidovits, ‘‘The Need to Create a New Technical Language for the Transfer
of Basic Scientific Information’’; pp. 316–20 in Transfer and Exploitation of Sci-
entific and Technical Information, EUR 7716. Edited by J. M. Gibb and D.
Nicolay. Commission of the European Communities, Luxembourg, 1982.
4
V. D. Glukhovsky, ‘‘Ancient, Modern and Future Concretes’’; pp. 1–9 in Pro-
ceedings of the First International Conference on Alkaline Cements and Concretes,
Edited by P. V. Krivenko. Vipol Stock Company, Kiev, Ukraine, 1994.
5
C. Shi, P. V. Krivenko, and D. M. Roy, Alkali-Activated Cements and Con-
cretes. Taylor & Francis, Abingdon, UK, 2006, 376pp.
6 31
M. Gordon, J. L. Bell, and W. M. Kriven, ‘‘Comparison of Naturally and
Synthetically Derived, Potassium-Based Geopolymers,’’ Ceram. Trans., 165, 95–
106 (2005).
7 32
J. P. Hos, P. G. McCormick, and L. T. Byrne, ‘‘Investigation of a Synthetic
Aluminosilicate Inorganic Polymer,’’ J. Mater. Sci., 37 [11] 2311–6 (2002).
8
A. P. Zosin, T. I. Priimak, and K. B. Avsaragov, ‘‘Geopolymer Materials
Based on Magnesia–Iron Slags for Normalization and Storage of Radioactive
Wastes,’’ At. Energy, 85 [1] 510–4 (1998).
9
K. Komnitsas, D. Zaharaki, and V. Perdikatsis, ‘‘Geopolymerisation of Low
Calcium Ferronickel Slags,’’ J. Mater. Sci., 42 [9] 3073–82 (2007).
10
N. Tsuyuki and K. Koizumi, ‘‘Granularity and Surface Structure of Ground
Granulated Blast-Furnace Slags,’’ J. Am. Ceram. Soc., 82 [8] 2188–92 (1999).
11
E. F. Osborn, R. C. DeVries, K. H. Gee, and H. M. Kraner, ‘‘Optimum
Composition of Blast-Furnace Slag as Deduced from Liquids Data for the Qua-
ternary System CaO–MgO–Al2O3–SiO2,’’ J. Metals, 6 [1] 33–45 (1954).
12
H. Wan, Z. Shui, and Z. Lin, ‘‘Analysis of Geometric Characteristics of GGBS
Particles and their Influences on Cement Properties,’’ Cem. Concr. Res., 34 [1] 133–
7 (2004).
13
P. Z. Wang, R. Trettin, and V. Rudert, ‘‘Effect of Fineness and Particle Size
Distribution of Granulated Blast-Furnace Slag on the Hydraulic Reactivity in
Cement Systems,’’ Adv. Cem. Res., 17 [4] 161–6 (2005).
14
R. T. Hemmings and E. E. Berry, ‘‘On the Glass in Coal Fly Ashes: Recent
Advances’’; pp. 3–38 in Fly Ash and Coal Conversion By-Products: Characteriza-
tion, Utilization, and Disposal IV, Edited by G. J. McCarthy. Materials Research
Society, Warrendale, PA, 1988.
15
J. C. Hower, R. F. Rathbone, J. D. Robertson, G. Peterson, and S. Trimble,
‘‘Petrology, Mineralogy, and Chemistry of Magnetically-Separated Sized Fly
Ash,’’ Fuel, 78 [2] 197–203 (1999).
16
H. W. Nugteren, ‘‘Coal Fly Ash: From Waste to Industrial Product,’’ Part.
Part. Syst. Charact., 24 [1] 49–55 (2007).
17
W. K. W. Lee and J. S. J. van Deventer, ‘‘Structural Reorganisation of Class F
Fly Ash in Alkaline Silicate Solutions,’’ Colloids Surf. A, 211 [1] 49–66 (2002).
18
J. G. S. van Jaarsveld, ‘‘The Physical and Chemical Characterisation of Fly
Ash Based Geopolymers’’; Ph.D. Thesis, University of Melbourne, Australia,
2000.
19
L. M. Keyte, G. C. Lukey, and J. S. J. van Deventer, ‘‘The Effect of Coal Ash
Glass Chemistry on the Tailored Design of Waste-Based Geopolymeric Products’’;
in WasteEng 2005. CD-ROM Proceedings, Edited by A. Nzihou. Albi, France,
2005.
20
A. Fernández-Jiménez and A. Palomo, ‘‘Characterisation of Fly Ashes.
Potential Reactivity as Alkaline Cements,’’ Fuel, 82 [18] 2259–65 (2003).
21
D. S. Perera, C. L. Nicholson, M. G. Blackford, R. A. Fletcher, and R. A.
Trautman, ‘‘Geopolymers Made Using New Zealand Flyash,’’ J. Ceram. Soc.
Jpn., 112 [5] S108–11 (2004).
22
H. Xu, G. C. Lukey, and J. S. J. van Deventer, ‘‘The Activation of Class C-,
Class F- Fly Ash and Blast Furnace Slag Using Geopolymerisation’’; pp. 797–819
in Proceedings of 8th CANMET/ACI International Conference on Fly Ash, Silica
Fume, Slag and Natural Pozzolans in Concrete, Edited by V. M. Malhotra.
American Concrete Institute, Las Vegas, NV, 2004.
23
P. Chindaprasirt, T. Chareerat, and V. Sirivivatnanon, ‘‘Workability and
Strength of Coarse High Calcium Fly Ash Geopolymer,’’ Cem. Concr. Compos., 29
[3] 224–9 (2007).
24
A. Roy, P. J. Schilling, and H. C. Eaton, ‘‘Alkali Activated Class C Fly Ash
Cement’’; U.S. Patent 5,565,028 1996.
25
G. C. Lukey, P. A. Mendis, J. S. J. van Deventer, and M. Sofi, ‘‘Advances in
Inorganic Polymer Concrete Technology’’; in Concrete Mix Design, Quality Con-
trol and Specification. Appendix A, 3rd edition, Edited by K. W. Day. Routledge,
London, 2006.
26
H. J. H. Brouwers and R. J. van Eijk, ‘‘Fly Ash Reactivity: Extension and
Application of a Shrinking Core Model and Thermodynamic Approach,’’ J.
Mater. Sci., 37 [10] 2129–41 (2002).
27
A. Fernández-Jiménez, A. Palomo, I. Sobrados, and J. Sanz, ‘‘The Role
Played by the Reactive Alumina Content in the Alkaline Activation of Fly Ashes,’’
Micropor. Mesopor. Mater., 91 [1–3] 111–9 (2006).
3869
C. A. Rees, J. L. Provis, G. C. Lukey, and J. S. J. van Deventer, ‘‘In Situ ATR-
FTIR Study of the Early Stages of Fly Ash Geopolymer Gel Formation,’’ Lan-
gmuir, 23 [17] 9076–82 (2007).
29
C. A. Rees, J. L. Provis, G. C. Lukey, and J. S. J. van Deventer, ‘‘Geopolymer
Gel Formation with Seeded Nucleation,’’ Colloids Surf. A, 318 [1–3] 97–105
(2008).
30
L. Weng, K. Sagoe-Crentsil, T. Brown, and S. Song, ‘‘Effects of
Aluminates on the Formation of Geopolymers,’’ Mater. Sci. Eng. B, 117 [2]
163–8 (2005).
P. Duxson, G. C. Lukey, F. Separovic, and J. S. J. van Deventer, ‘‘The Effect
of Alkali Cations on Aluminum Incorporation in Geopolymeric Gels,’’ Ind. Eng.
Chem. Res., 44 [4] 832–9 (2005).
J. G. S. van Jaarsveld and J. S. J. van Deventer, ‘‘Effect of the Alkali Metal
Activator on the Properties of Fly Ash-Based Geopolymers,’’ Ind. Eng. Chem.
Res., 38 [10] 3932–41 (1999).
33
B. H. W. S. de Jong and G. E. Brown, ‘‘Polymerization of Silicate and Al-
uminate Tetrahedra in Glasses, Melts, and Aqueous Solutions—I. Electronic
Structure of H6Si2O7, H6AlSiO1 2
7 , and H6Al2O7,’’ Geochim. Cosmochim. Acta,
44 [3] 491–511 (1980).
34
J. P. Hamilton, S. L. Brantley, C. G. Pantano, L. J. Criscenti, and J. D. Ku-
bicki, ‘‘Dissolution of Nepheline, Jadeite and Albite Glasses: Toward Better Mod-
els for Aluminosilicate Dissolution,’’ Geochim. Cosmochim. Acta, 65 [21] 3683–702
(2001).
35
A. E. Blum and A. C. Lasaga, ‘‘The Role of Surface Speciation in the Dis-
solution of Albite,’’ Geochim. Cosmochim. Acta, 55 [8] 2193–201 (1991).
36
E. H. Oelkers and S. R. Gislason, ‘‘The Mechanism, Rates and Consequences
of Basaltic Glass Dissolution: I. An Experimental Study of the Dissolution
Rates of Basaltic Glass as a Function of Aqueous Al, Si and Oxalic Acid Con-
centration at 251C and pH 5 3 and 11,’’ Geochim. Cosmochim. Acta, 65 [21] 3671–
81 (2001).
37
S. K. Lee and J. F. Stebbins, ‘‘Disorder and the Extent of Polymerization in
Calcium Silicate and Aluminosilicate Glasses: O-17 NMR Results and Quantum
Chemical Molecular Orbital Calculations,’’ Geochim. Cosmochim. Acta, 70 [16]
4275–86 (2006).
38
E. H. Oelkers, J. Schott, and J. L. Devidal, ‘‘The Effect of Aluminum, pH, and
Chemical Affinity on the Rates of Aluminosilicate Dissolution Reactions,’’ Geoc-
him. Cosmochim. Acta, 58 [9] 2011–24 (1994).
39
E. H. Oelkers, ‘‘General Kinetic Description of Multioxide Silicate
Mineral and Glass Dissolution,’’ Geochim. Cosmochim. Acta, 65 [21] 3703–19
(2001).
40
A. E. Blum and A. C. Lasaga, ‘‘Role of Surface Speciation in the Low-Tem-
perature Dissolution of Minerals,’’ Nature, 331 [6155] 431–3 (1988).
41
B. R. Bickmore, K. L. Nagy, A. K. Gray, and A. R. Brinkerhoff, ‘‘The Effect
of Al(OH) 4 on the Dissolution Rate of Quartz,’’ Geochim. Cosmochim. Acta, 70 [2]
290–305 (2006).
42
P. M. Dove, ‘‘The Dissolution Kinetics of Quartz in Sodium Chloride Solu-
tions at 251 to 3001C,’’ Am. J. Sci., 294 [6] 665–712 (1994).
43
J. F. Stebbins and Z. Xu, ‘‘NMR Evidence for Excess Non-Bridging Oxygen
in an Aluminosilicate Glass,’’ Nature, 390 [6655] 60–2 (1997).
44
C. A. Rees, ‘‘Mechanisms and Kinetics of Gel Formation in Geopolymers’’;
Ph.D. Thesis, University of Melbourne, 2007.
45
P. Duxson, J. L. Provis, G. C. Lukey, and J. S. J. van Deventer, ‘‘The Role of
Inorganic Polymer Technology in the Development of ‘Green Concrete’,’’ Cem.
Concr. Res., 37 [12] 1590–7 (2007).
46
W. M. Kriven, C. A. Kelly, and D. C. Comrie, ‘‘Geopolymers for Structural
Ceramic Applications, Air Force Office of Scientific Research Report FA9550-04-
C-0063, 2006, 144pp. http://stinet.dtic.mil/cgi-bin/GetTRDoc?AD=ADA463559
&Location=U2&doc=GetTRDoc.pdf.
47
P. Duxson, G. C. Lukey, and J. S. J. van Deventer, ‘‘Thermal Evolution of
Metakaolin Geopolymers: Part 1—Physical Evolution,’’ J. Non-Cryst. Solids, 352
[52–54] 5541–55 (2006).
48
P. Duxson, G. C. Lukey, and J. S. J. van Deventer, ‘‘The Thermal Evolution
of Metakaolin Geopolymers: Part 2—Phase Stability and Structural Develop-
ment,’’ J. Non-Cryst. Solids, 353 [22–23] 2186–200 (2007).
49
X. P. Feng, H. H. Sun, and X. M. Liu, ‘‘Sialite Technology,’’ Adv. Mater. Res.,
11–12, 615–8 (2006).
50
N. Bouzoubaâ, M. H. Zhang, A. Bilodeau, and V. M. Malhotra, ‘‘The Effect
of Grinding on the Physical Properties of Fly Ashes and a Portland Cement
Clinker,’’ Cem. Concr. Res., 27 [12] 1861–74 (1997).
51
N. Bouzoubaâ, M. H. Zhang, V. M. Malhotra, and D. M. Golden, ‘‘Blended
fly Ash Cements—A Review,’’ ACI Mater. J., 96 [6] 641–50 (1999).
52
R. Nowak, ‘‘Build ‘Em High, and Make Them Green,’’ N. Scientist, 197 [2640]
28–9 (2008). &