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Fundamentals of Geopolymers and Related Alkali Activated Materials

Article in Materials Science Forum · January 2015

DOI: 10.4028/www.scientific.net/MSF.803.144

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Materials Science Forum Vol. 803 (2015) pp 144-147 Submitted: 10.07.2014
Online available since 2014/Aug/28 at www.scientific.net Accepted: 11.07.2014
© (2015) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/MSF.803.144

Fundamentals of Geopolymers and Related Alkali Activated Materials

J.Temuujin, A.Minjigmaa, U.Bayarzul, Ts.Zolzaya, B.Davaabal, J.Amgalan
Institute of Chemistry and Chemical Technology, Mongolian Academy of Sciences
Ulaanbaatar 51, Mongolia

Keywords: Geopolymer binder, alkali-activated materials, coal combustion by products,

Abstract.With the increasing rate of depletion of natural raw materials for production of building
materials, their sustainable usage is clearly an important topic for consideration. For instance, 1
tonne ordinary Portland cement (OPC) requires 1.7 tonnes of raw materials, 1.0 tonne of coal and
100 kWh of electricity. One tonne of cement emits 0.8 - 1 tonne of CO2 into atmosphere globally
contributing ~5% of total manmade carbon dioxide. Therefore, the development of new,
sustainable, low carbon footprint construction materials is an important task for materials scientists
and civil engineers. One type of binder that is attracting particular attention around the world is
alkali-aluminosilicate chemistry based material the so-called geopolymers.
In this presentation we will discuss the fundamentals of geopolymer chemistry and the similarities
to and differences from conventional alkali activated materials chemistry.
Particular attention will be given to our latest results on the preparation of geopolymer type paste
and concrete from fly ash. Mechanical activation of fly ash caused a decrease in porosity with a
partial amorphisation of the crystalline constituents. Geopolymer type paste prepared from 30
minute milled Darkhan pond ash showed increase in 7 day compressive strengths by 7 times
reaching of 15.4 (4.6) MPa.
Introduction
With increasing human population, the sustainable use of raw materials is becoming an important
issue for our continued future development. Construction and building materials production requires
a significant consumption og natural resources. For instance, 1 tonne ordinary Portland cement
(OPC) requires 1.7 tonnes of raw materials, 1.0 tonne of coal and 100 kWh of electricity whilst
emitting 0.8 - 1 tonne of CO2 into atmosphere. Globally this is around 5% of total manmade carbon
dioxide [1]. Therefore, reducing of carbon footprint from OPC production by substituting it with
another material is an important challenge for researchers. In the last twenty years many materials
that can be substitute OPC have been proposed [2]. One such alternative cement material is alkali
activated cement or geopolymer. Geopolymers are amorphous to semi-crystalline 3-dimensional
aluminosilicate materials prepared by alkali activation and low to moderate temperature curing of
aluminosilicates, either naturally occurrring or residues from industrial processes. For many years
geopolymer materials have attracted much interest within the scientific community and have been
the subject of many review papers [3-5].
Historical background
Davidovits coined the term "Geopolymer” in 1979, published the first paper in 1991 [7] and in 1985
secured the first patent on “Pyrament” cement [6].
According to Davidovits, the geopolymers are chains or networks of mineral molecules linked with
co-valence bonds. They are X-ray amorphous at ambient and medium temperatures and X-ray
crystalline at temperatures >500°C. It contains various combinations of the following molecular
units :
-Si-O-Si-O-siloxo, poly(siloxo),
-Si-O-Al-O-sialate, poly(sialate),
-Si-O-Al-O-Si-sialate-siloxo, poly(sialate-siloxo),

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 Materials Science Forum Vol. 803 145

-Si-O-Al-O-Si-O-Si-O-sialate-disiloxo, poly(sialate-disoloxo),
-Fe-O-Si-O-Al-O-Si-O-ferro-sialate, poly(ferro-sialate),
-P-O-P- 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),
-Al-O-P-O- alumino-phospho, poly(alumino-phospho),
-(R)-Si-O-Si-O-(R) organo-siloxo, poly-silicone.
However, the same type alkali activated ground blast furnace slag based binder materials were
developed by Glukhovskii et al, in 1950’s [8]. Those material showed almost the same
characteristics as those of Davidovits’s geopolymer other than showing a semi amorphous zeolite
type structure. Glukhovskii used the waste from domestic chemical factories containing up to 50%
NaOH as alkaline activator. In the former Soviet Union alkali activated materials had some
practical application such as precast panel. A multistorey appartment block was built in Lipetske
(Russian Federation) in 1987 using alkali activated GBFS based concrete. Fig.1 shows that building
in 2012.

Fig.1 Alkali activated ground blast furnace slag used geopolymer type concrete building
This picture suggests that the panels made from ground blast furnace slag based alkali activated
concrete remains in good condition after 25 years of exposure to a comparatively harsh climate.
Davidovits suggested that in a true geopolymer the Al atoms must have tetrahedral coordination.
This is true for geopolymers prepared from metakaolin or synthesized from chemical reagents but
not for those made from alkali activated ground furnace slag based materials as not all Al are in
tetrahedral coordination and there is a large calcium content. The presence calcium should results
formation of calcium silicate hydrate (C-S-H) phase. Therefore, there questions arises are:
- Are such alkali activated materials geopolymers?
- Should materials containing C-S-H phase classed as geopolymers?
- If the resulting material contains octahedrally coordinated Al as unreacted glassy or crystalline
phases can they be regarded as geopolymers?
- Can fly ash be regarded as a raw material for geopolymers?
The answer of these questions could clarify difference between geopolymers and alkali activated
materials. It is almost impossible to prepare alkali activated materials that all Al in tetrahedral
coordination. Formation of geopolymers from metakaolin includes more than ten overlapping
mechanisms including dissolution, oligomerisation, polycondensation, gelation, hardening etc. The
146 Geopolymer and Green Technology Materials

common features of the geopolymers and alkali activated materials are dissolution in the alkaline
condition, polycondensation and hardening. Therefore, we cannot follow Davidovits’s rule of
defining geopolymers as containing tetrahedrally coordination Al for non-calcium containing raw
materials. The term “Geopolymers” or “alkali activated cement” should be used for those materials
where the alkaline dissolution -polycondensation - hardening mechanism takes place.

Preparation of alkali activated materials from pond ashes.

Generally, thermal power station coal combustion by-products can be divided into different
catagories. Namely:
-Fly Ash — Pulverized ash extracted from flue gases by any suitable process such as by cyclone
separator or electro-static precipitator. Typically fine particle sizes.
-Bottom Ash — Pulverized fuel ash collected from the bottom of boilers by any suitable process.
Coarser particle sizes.
-Pond Ash — Fly ash or bottom ash or both mixed in any proportion and conveyed in the form of
water slurry and deposited in pond or lagoon. Weathered particles of all sizes.
Fly ash is the best raw material for preparation of geopolymers due to the minimal water content
and finer particle size. Pond ash is considered the least suitable material because of the high water
content and high porosity caused by dissolution of soluble components of fly ash in the water. For
instance the BET specific surface area of fly ash is about 2 m2/g, but up to 30 m2/g in pond ashes.
Such highly porous structures adsorb a large amount of alkaline liquid resulting in high amounts of
sodium hydroxide in the geopolymer structure which results in weak mechanical properties. In
order to destroy the porous microstructure mechanical activation treatment was applied. Mechanical
treatment was performed with a ring type vibratory mill. Mechanical activation of the pond ash
caused not only crush of the porous structure, but also a partial amorphization of the crystalline
constituents of ash such as mullite.
Fig.2 shows XRD patterns of pond ash, 30 minute mechanically treated pond ash and geopolymer
prepared from 30 minute ground fly ash.

Fig.2. XRD patterns of raw pond ash (a), 30 min milled ash (b) and geopolymer (c).
 Materials Science Forum Vol. 803 147

Raw pond ash showed quartz, hematite and mullite as crystalline phases. In the XRD pattern of the
30 minute milled sample one could observe broadening of the mullite patterns which likely suggest
a partial amorphisation of its structure.
Table 1 indicates the mechanical properties of the pond ash based geopolymer type paste. Clear
indication of the destruction of the porous microstructure comes from the significant decrease in
liquid:solid ratio. Just 5 minutes of grinding caused a 25% decrease in the liquid:solid ratio. At the
same time increase in densities and compressive strengths of the geopolymers were observed. The
highest compressive strength was observed for 30 minute milled geopolymer type paste.
Table 1. Mechanical properties of the milled Darkhan pond ash based geopolymer type pastes.
Sample Activation Liquid:Solid Density, Compressive
3
time, (g/sm ) strength(MPA)
(min)
0 0.44 1.24(0.03) 3.25(1.7)
5 0.33 1.26(0.03) 3.5(1.73)
Darkhan 10 0.3 1.43(0) 7.25(3.8)
20 0.33 1.44(0) 8.33(1.53)
30 0.32 1.4(0) 15.4(4.6)

Presented results clearly indicate that the microstructure of the initial raw materials show very
strong influence in alkali activated materials properties and it can be manipulated by preliminary
treatment such as mechanical activation to change initial microstructure.

Conclusions
The term “Geopolymer” or “alkali activated cement” should use for those materials where alkaline
dissolution - polycondensation - hardening mechanisms takes place.
The potential for using CCBPs depends on the chemical, mineralogical composition and physico-
chemical properties of the ash compounds. Pond ashes are the least suitable raw materials because
of water content and high porosity. Porosity of the pond ashes can be reduced by 5-30 minute
mechanical activation. By using mechanically activated pond ashes geopolymer type binders with
compressive strength of 15 MPa can be prepared.

References
[1] de Quervain B. Resource Efficiency in Cement Production, Presented in Smart Energy
Strategies Conference 2011, Zurich, Switzerland, 22 September 2011,
http://www.esc.ethz.ch/ses11/DeQuervain_presentation.pdf
[2] E.Gartner, Industrially interesting approaches to ‘‘low-CO2’’ cements, Cement and Concrete
Research 34 (2004) 1489–1498
[3] Komnitsas K, Zaharaki D. Geopolymerisation: a review and prospects for the minerals industry.
Minerals Engineering, 20, (2007) 1261–77.
[4] Duxson P, Fernández-Jiménez A, Provis JL, Lukey GC, Palomo A, Van Deventer JSJ.
Geopolymer technology: the current state of the art. Journal of Materials Science, 42 (2007)
2917–33.
[5] Pacheco-Torgal F, Abdollahnejad Z, Camões AF, Jamshidi M, Ding Y, Durability of alkali-
activated binders: A clear advantage over Portland cement or an unproven issue?, Construction
and Building Materials, 30 (2012) 400–05
[6] J.Davidovits and Sawyer, US Patent 4,509,985
[7] J.Davidovits, Geopolymers: Inorganic polymeric new materials, Journal of thermal analysis, 37
(1991) 1633-1656
[8] V.Glukhovskii, “Soil silicates”, Gosstroiizdat, 1959.
 Geopolymer and Green Technology Materials
10.4028/www.scientific.net/MSF.803

Fundamentals of Geopolymers and Related Alkali Activated Materials

10.4028/www.scientific.net/MSF.803.144

DOI References
[2] E. Gartner, Industrially interesting approaches to 'low-CO2', cements, Cement and Concrete Research 34
(2004) 1489-1498.
http://dx.doi.org/10.1016/j.cemconres.2004.01.021

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