What is a geopolymer?

Introduction
5 Apr 2006
updated: August 17, 2012

Geopolymers are chains or networks of mineral molecules linked with co-valent

bonds. They have following basic characteristics:

a) Nature of the hardened material:

 X-ray amorphous at ambient and medium temperatures

 X-ray crystalline at temperatures > 500°C

b) Synthesis Routes:

 alkaline medium (Na, K, Ca) hydroxides and alkali-silicates yielding

poly(silicates) – poly(siloxo) type or poly(silico-aluminates) – poly(sialate)
type
 acidic medium (Phosphoric acid) yielding poly(phospho-siloxo) and
poly(alumino-phospho) types

As an example, one of the geopolymeric precursors, MK-750 (metakaolin) with

its alumoxyl group –Si-O-Al=O, reacts in both systems, alkaline and acidic.
Same for siloxo-based and organo-siloxo-based geopolymeric species that also
react in both alkaline and acidic medium.

Geopolymer Terminology

In the late 1970’s, Joseph Davidovits , the inventor and developer of

geopolymerization, coined the term “geopolymer” to classify the newly
discovered geosynthesis that produces inorganic polymeric materials now used
for a number of industrial applications. He also set a logical scientific
terminology based on different chemical units, essentially for silicate and
aluminosilicate materials, classified according to the Si:Al atomic ratio:

Si:Al = 0, siloxo
Si:Al = 1, sialate (acronym for silicon-oxo-aluminate of Na, K, Ca, Li)
Si:Al = 2, sialate-siloxo
Si:Al = 3, sialate-disiloxo
Si:Al > 3, sialate link.
This terminology was presented to the scientific community at a IUPAC
conference in 1976. See for details in the Library the paper Milestone Paper
IUPAC-76

In the introduction of his book on alkali-geopolymer cement, the alkali-cement

scientist John Provis, challenged the use of the word ‘sialate’ arguing that “…
the term ‘sialate’ was already in use (since the 1950s) to describe any of the
salts of organic sialic acid …” He simply forgot to mention that long before 1950
geology has been using extensively the term ‘sialic’, for example in ‘sialic
metamorphic rocks‘, or ‘the oceanic crust is mostly basaltic and the continental
crust is mostly sialic, meaning the rocks, such as granite, contain high amounts
of aluminum and silica‘. Not to forget the fact that fly ashes were and still are
commonly classified into three entities: calcic-, ferric- and sialic-groups; the
sialic component results from the %weight of (SiO 2 + Al2O 3 + TiO2). There exists
another example, namely the well known term ‘SIALON’, a specialist class of
high temperature refractory materials, acronym of silicon-aluminum-oxo-nitride,
i.e. a scientific logical terminology. The geopolymeric ‘sialate‘ term proceeds
from the same scientific logic (it is the acronym of silicon-oxo-aluminate), in
contrast with the organic molecule ‘sialic acid’ that was derived from an ancient
Greek word meaning ‘saliva’, with no scientific association. In fact, for our
geopolymer molecules we write poly(sialate) / polysialate or poly(sialate-siloxo),
a terminology never used in biochemistry. We shall therefore keep our
terminology, use it and promote it without any restriction.

Geopolymers comprise following molecular units (or chemical groups):

-Si-O-Si-O- siloxo, poly(siloxo)

-Si-O-Al-O- sialate, poly(sialate)
-Si-O-Al-O-Si-O- sialate-siloxo, poly(sialate-siloxo)
-Si-O-Al-O-Si-O-Si-O- sialate-disiloxo, poly(sialate-disiloxo)
-P-O-P-O- phosphate, poly(phosphate)
-P-O-Si-O-P-O- phospho-siloxo, poly(phospho-siloxo)
-P-O-Si-O-Al-O-P-O- phospho-sialate, poly(phospho-sialate)
-(R)-Si-O-Si-O-(R) organo-siloxo, poly-silicone
-Al-O-P-O- alumino-phospho, poly(alumino-phospho)
-Fe-O-Si-O-Al-O-Si-O- ferro-sialate, poly(ferro-sialate)

Geopolymers are presently developed and applied in 10 main classes of

materials:

 Waterglass-based geopolymer, poly(siloxonate), soluble silicate, Si:Al=1:0

 Kaolinite / Hydrosodalite-based geopolymer, poly(sialate) Si:Al=1:1
 Metakaolin MK-750-based geopolymer, poly(sialate-siloxo) Si:Al=2:1
 Calcium-based geopolymer, (Ca, K, Na)-sialate, Si:Al=1, 2, 3
  Rock-based geopolymer, poly(sialate-multisiloxo) 1< Si:Al<5
 Silica-based geopolymer, sialate link and siloxo link in poly(siloxonate)
Si:Al>5
 Fly ash-based geopolymer
 Ferro-sialate-based geopolymer
 Phosphate-based geopolymer, AlPO4-based geopolymer
 Organic-mineral geopolymer

World-wide increase in geopolymer

research
9 Aug 2010
Twenty five years long, geopolymer science was studied in very few laboratories
and institutions. It is only during the last ten years that we notice a strong
increase in geopolymer research. The actual situation was presented by Prof. J.
Davidovits in his 2010 Geopolymer Camp Keynote: State of the Geopolymer
2010. The following map shows the evolution of the number of laboratories
involved in geopolymer research, from 1999 to 2010.

The number of scientific papers dealing with geopolymer science & technology
is following an exponential growth. The chart displays the evolution of the
number of geopolymer papers published from 1991 onwards (publication of
Davidovits’ reference paper in J. Thermal Analysis), up to 2013, referenced
in Science Direct + SpringerLink + Wiley + DOAJ + ACS under the keyword
“geopolymer”. Other publications, such as conference proceedings are not
accounted for in these statistical tools. The exponential growth of published
scientific papers is confirmed for 2014.

About geopolymerization
5 Apr 2006

In 1937 W. L. Bragg published a method for classifying all kinds of silicates and
their crystal structures based on the concept of the ionic theory by L. Pauling.
The fundamental unit is a tetrahedral complex consisting of a small cation such
as Si4+, or Al 3+ in tetrahedral coordination with four oxygens (Pauling’s first rule).
Many textbooks explain the geometry of the SiO 4-tetrahedron and other mineral
structures as determined by the relative sizes of the different ions.
This ionic coordination representation is no longer adapted to the
requirements of geopolymer chemistry that is governed by covalent
bonding mechanisms.

Not ionic (tetrahedral) but covalent !

In the figure below, six atomic arrangements are used to illustrate the silicate
ionic structure on the one hand, and the siloxonate/sialate covalent construction
on the other hand.
a) Electrons distribution: in the external layer of the atoms Si, O, Al and Na.
The electrovalence rules command the creation of the octet (8 electrons in the
external shell) either by donating electrons (donator) or by receiving electrons
(receptor), as follows:
– Si has 4 electrons. It is a donator or an acceptor (tetra-valence).
– O has 6 electrons. It is a receptor (di-valence).
– Al has 3 electrons. It is a donator in acidic medium (tri-valence) and a receptor
in alkaline solution (tetra-valence).
– Na has 1 electron. It is a donator (mono-valence).

b) Ionic concept tetrahedron, coordination: The ions (Si 4+, 4O–) build the
single tetrahedron. Si donates 4 electrons to the 4 oxygens and turns into a
small cation Si 4+. Si is tetracoordinated with the 4 oxygens. To achieve anionic
stability, each oxygen needs an eighth electron supplied by a metal (Na, K, Ca,
Mg, Fe, etc.) or another Si, not shown on the Figure.

c) Ionic concept: By the mutual sharing of one oxygen anion O 2-, two or more
tetrahedra may link to form polyanionic groups.

d) Covalent concept: The molecule (SiO 4) results from the co-sharing of

electrons between one Si atom and the four surrounding oxygens yielding Si-O
covalent bonds (tetravalence). The ortho-siloxonate molecule (SiO 4)4- requires
additional metallic ion donators (Na, K, Ca, Mg, Fe) not shown on the figure.

e) Covalent concept: The polycondensation into di-siloxonate and higher

polymeric siloxonates occurs by additional co-sharing of electrons between Si
and O. The di-siloxonate molecule (Si 2O7)6- requires additional metallic ion
donators (Na, K, Ca, Mg, Fe).

f) Covalent concept: The formation of the ortho-sialate molecule with the

covalent bond Si-O-Al- occurs in alkaline medium. The Al atom takes the single
electron pertaining to a metalloid (Na for example) and becomes tetra-valent,
like Si, with an additional negative electrostatic charge. The Na+ cation is
strongly attached to the sialate molecule and balances the negative charge.

The differences between the ionic concept (coordination) and the covalent
macromolecular bonding are profound. The double tetrahedron in structure (c) is
sharing one oxygen anion O 2-, whereas in the di-siloxonate molecule of structure
(e), the covalent bond is achieved through Si and O co-sharing only one
electron. This results in stronger bond within the latter structure.

Geopolymerization starts with oligomers

The geo-chemical syntheses are carried out through oligomers (dimer, trimer,
tetramer, pentamer) which provide the actual unit structures of the three
dimensional macromolecular edifice. See in J. Davidovits’ book, Geopolymer
Chemistry & Applications , the Chapters 2, 5, 6, 7 and 8.

Example of geopolymerization with metakaolin MK-750

Excerpt from Chapter 8 of Geopolymer Chemistry & Applications:
It involves 3 phases:
– alkaline depolymerization of the poly(siloxo) layer of kaolinite
– formation of the ortho-sialate (OH) 3-Si-O-Al-(OH) 3 molecule
– polymerization (polycondensation) into higher oligomers and polymers

The geopolymerization kinetics for Na-poly(sialate-siloxo) and K-poly(sialate-

siloxo) are slightly different. This is probably due to the different dimensions of
the Na + and K+ cations, K +being bigger than Na +.

Chemical mechanism with Al(V) -Al=O alumoxyl (Al V coordination in MK-

750 metakaolin)

The chemical mechanism can be interpreted in the following way, with NaOH or
KOH (steps 1 to 6-7) :

Step 1: alkalination and formation of tetravalent Al in the side group sialate -Si-
O-Al-(OH) 3-Na +,
Step 2: alkaline dissolution starts with the attachment of the base OH- to the
silicon atom, which is thus able to extend its valence sphere to the penta-
covalent state,

Step 3: the subsequent course of the reaction can be explained by the cleavage
of the siloxane oxygen in Si-O-Si through transfer of the electron from Si to O,
formation of intermediate silanol Si-OH on the one hand, and basic siloxo Si-O-
on the other hand.

Step 4: further formation of silanol Si-OH groups and isolation of the ortho-
sialate molecule, the primary unit in geopolymerization.

Step 5: reaction of the basic siloxo Si-O- with the sodium cation Na + and
formation of Si-O-Na terminal bond.

Step 6a: condensation between ortho-sialate molecules, reactive groups Si-

ONa and aluminum hydroxyl OH-Al, with production of NaOH, creation of cyclo-
tri-sialate structure, whereby the alkali NaOH is liberated and reacts again and
further polycondensation into Na-poly(sialate) nepheline framework.
Step 6b: in the presence of waterglass (soluble Na- polysiloxonate) one gets
condensation between di-siloxonate Q 1 and ortho-sialate molecules, reactive
groups Si-ONa, Si-OH and aluminum hydroxyl OH-Al-, creation of ortho-sialate-
disiloxo cyclic structure, whereby the alkali NaOH is liberated and reacts again.

Step 7: further polycondensation into Na-poly(sialate-disiloxo) albite framework

with its typical feldspar crankshaft chain structure.

Scientific means of investigation

5 Apr 2006

X-rays diffraction spectra of hardened geopolymeric materials (resins and

cements) do not supply accurate information (amorphous structure). High-
resolution MAS-NMR (Nuclear Magnetic Resonance) spectroscopy of 29Si
and 27Al is a very powerful tool that provides useful structural data.

For more updated information, see in Davidovits’ book, Geopolymer Chemistry

& Applications , the Chapter 4. You may also download previous scientific
papers #12 J. Thermal Analysis , #3 NASTS award  or #8 Alkaline Cements and
Concretes . Other scientific means of investigation, including DTA, XRF,
ANOVA, liquid NMR, FTIR spectroscopy, SEM, TEM, mechanical resistance,
fatigue under stress and cycles, load-deflection, thermal resistance, leaching
behavior, hydraulic conductivity, microbial stability, are discussed in the various
papers presented at the Geopolymer World Congress and published in
the Proceedings of Geopolymer 2005 .

Evidence of oligomer units by NMR

Low molecular elements (monomer, dimer, trimer, tetramer, pentamer) are
called oligomers. Oligo-sialate designates the monomer ortho-sialate, the dimer
is disialate, etc.; same for oligo(sialate-siloxo) and oligo(sialate-disiloxo). At the
beginning of geopolymer research, Joseph Davidovits in 1976 and afterwards
for at least 25 years, assumed that the geo-chemical syntheses occurred
through hypothetical oligomers (dimer, trimer). Further polycondensation of
 these hypothetical building units provided the actual structures of the three
dimensional macromolecular edifice as displayed in the Figure below. Review
papers published at the First Geopolymer Conference in 1988, and at the
second, 11 years later, in 1999, could not present scientific details describing
the actual reaction mechanism.

Reaction mechanism for sialate and sialate-siloxo species, described as

hypothetical by Davidovits in 1988.

It has been the merit of T.W. Swaddle and his team (North M.R. and Swaddle
T.W., (2000), Kinetics of Silicate Exchange in Alkaline Aluminosilicate
Solutions, Inorg. Chem., 39, 2661-2665) to demonstrate the existence of soluble
aluminosilicate species in solution in relatively high concentrations and high pH.
One major improvement in their research was that their study was carried out at
very low temperatures as low as -9°C. Indeed, it was discovered that the
polymerization of oligo-sialates was taking place on a time scale of around 100
milliseconds, i.e. 100 to 1000 times faster than the polymerization of ortho-
silicate, oligo-siloxo units. At room temperature or higher, the reaction is so fast
that it cannot be detected with conventional NMR equipment.
 Five ortho-sialate solute species isolated in KOH solutions, after North and
Swaddle (2000).

The hypothetical oligomers set forth in geopolymer synthesis are no longer

virtual molecules. They actually exist in soluble forms in concentrated solutions
at high pH. Swaddle’s study confirms the polymerization mechanisms tentatively
reported earlier by Davidovits (1976) with linear oligo-sialate, oligo(sialate-
disiloxo) and rings or cycles, as starting geopolymer building units.

Examples of geopolymer frameworks

5 Apr 2006
Uptdated: August 28, 2012.

Geopolymerization forms aluminosilicate frameworks which are similar to those

of rock-forming minerals. Yet there are major differences. We simulated a
theoretical structure for K-poly(sialate-siloxo) that was consistent with the NMR
spectra. It does not show the presence of water in the structure because we
only focused on the relationship between Si, Al, Na, K, atoms. Water is present
only at temperatures below 150-200°C, and numerous geopolymer industrial
and commercial applications do work at temperatures above 200°C, up to
1400°C. Nevertheless, scientists working on low temperature applications, such
as cements and waste management tried to pinpoint cations hydration and
water molecules. For example Barbosa et al.(2000) stressed the importance of
water for cement applications and their model was modified by Rowles (2004).
THis model is only valid for incompletely reacted geopolymer. It involves free Al-
OH groups that will later with time or with temperature evidently polycondense
with opposed Si-O-Na, into sialate bonds.

Fully geopolymerized models are very close to the original one proposed by
Davidovits (1994).

After dehydroxylation (and dehydration), generally above 250°C, geopolymers

are becoming more and more crystalline and above 500°C have X-rays
diffraction patterns and framework structures identical to their geological
analogues.
Portland Cement Chemistry vs.
Geopolymer Chemistry
5 Apr 2006
updated: August 17, 2012
Left: hardening of Portland cement (P.C.) through simple hydration of Calcium
Silicate into Calcium Di-Silicate hydrate and lime Ca(OH) 2.

Right: hardening (setting) of Geopolymer resin (GP) through poly-condensation

of Potassium Oligo-(sialate-siloxo) into Potassium Poly(sialate-siloxo) cross
linked network.

The Australian Geopolymer Alliance  outlines on his web site the following

statement:

(…) Davidovits developed the notion of a geopolymer (a Si/Al inorganic

polymer) to better explain these chemical processes and the resultant material
properties.
(…) To do so required a major shift in perspective, away from the classical
crystalline hydration chemistry of conventional cement chemistry
(…) To date this shift has not been well accepted by practitioners in the field of
alkali activated cements who still tend to explain such reaction chemistry in
portland cement terminology.

In his recent keynote lecture held at the Geopolymer Camp 2012 State of

Geopolymer R&D 2012 , Prof. J. Davidovits stated that the present situation,
which is prevailing among cement scientists, is a major obstacle to any
breakthrough and innovation in geopolymer cement/concrete technology and is
responsible for the slow implementation of any world-wide industrialization. See
also in the LIBRARY the paper #21 Geopolymer cement review 2013 .