EFFECT OF THE ALKALINE ACTIVATOR ON THE REFRACTORINESS OF A

GEOPOLYMER CONTAINNING METAKAOLIN AND FLY-ASH

The term geopolymer comprises a family of mineral binders with similar chemical
composition of the zeolite, but with a mixed microstructure: amorphous - semi crystalline.
The geopolymers are also called polysialates, formed by a large molecular chain (poly)
consisting of silicon, oxygen and aluminum. Sialate is an abbreviation for silicate-oxidealuminate. From the literature, the materials obtained by alkaline activation (or
geopolymerization) are mechanically resistant and exhibit high thermal and chemical
stability. These characteristics are reached faster than those of Portland cement manufactured
materials. Furthermore, the different relationships SiO2/Al2O3 allow the application of these
materials in different areas, such as bricks, thermal insulation, and encapsulation of
radioactive and toxic waste, foundry equipment and composites. It seems therefore evident
the importance of promoting the development of alternative materials, complying with the
same performance objectives. In addition, these new materials could be considered
sustainable, because they reach their final properties at temperatures not exceeding 100C and
can be produced from industrial wastes. The influence of alkaline activators (Na and K) in the
refractoriness of a geopolymer derived from metakaolin with additions of fly ash was
evaluated in this work by XRD and empirical refractoriness tests, in order to determine the
final behavior of compositions, related to different activators and fly ash content.

Keywords: geopolymer, alkaline activation, refractoriness, metakaolin, activators, fly ash

1. Introduction

The term geopolymer was created by Davidovits [1] in 1978 to point out a family of
mineral binders with similar chemical composition of the zeolite, but with a mixed
microstructure (from amorphous to semi crystalline), where the silica (SiO2) and alumina
(Al2O3), constituents of aluminosilicates, react each other in a highly alkaline, organizing
themselves alternately in three dimensions by sharing of oxygen atoms forming bonds of the
type Si-O-Al-O, SiO-Al-O-Si-O or Si-O-Al-O -Si-O-Si-O. The geopolymers are also known
polysialates (large molecular chain consisting of silicon, oxygen and aluminum). Sialate is an
abbreviation for silicon-aluminate-oxide.

Since 1972 Davidovits [2] worked with kaolinite as a raw material together with alkalis
such as NaOH and KOH for the production of geopolymers. However, he changed later
(1978) to kaolinite calcined at 750C for 6 hours, metakaolin, as a raw material which gave
the best performance geopolymer.
The geopolymeric binders allow applications in virtually all fields of industry, because
among its properties, have high mechanical strength, resistance to freeze-thaw, high chemical
inertness and excellent fire behavior, may be considered as refractory materials [3].
Thus, in principle, aluminosilicates such as slag, fly ash, volcanic ash and dust from tile
or brick are potential starting materials for alkaline activation, because they have a previous
heat treatment [4, ].
It has been observed in several studies, a high degree of thermal stability of
geopolymers, especially in K-polysialates with melting point in the range of 1400C [6].
However, geopolymers for applications at temperatures between 1000 and 1200C were
also obtained with Na activators for applications such as thermal insulation [7]. Another
factor mentioned in the literature that may partially explain the superior behavior of
geopolymers, obtained with the addition of fly ash when exposed to high temperatures, is
related to the sintering of unreached particles of fly ash during the geopolymerization [8].

2. Materials and methods

The experimental development of this work used as raw materials: metakaolin HP

(HPMK), supplied by Metacaulim do Brasil Company, metakaolin obtained from the
calcination of Minasolo kaolin (MSMK) at 750C for 6 hours in a muffle EDG 3000, fly ash
class F (FA) provided by Tractebel Energia, alkaline activators NaOH (commercial), KOH
supplied by Dinmica Qumica, sodium silicate alkaline (SSA) and potassium silicate (PS),
both provided by Unaprosil.

2.1 Alkaline activators and molar ratios between components

The alkaline activators more used to obtain geopolymeric materials are sodium or
potassium hydroxide, sodium carbonate, sodium or potassium silicates, and especially
mixtures thereof. Based on the zeolits chemistry, Davidovits [9] suggests various limits and
molar ratios aiming to improve the final properties of geopolymers, such as durability and
strength.

 Activators:

SiO2 /Na2O = 1.85

Precursors:

0.20 < Na 2O/SiO2 < 0.48

3.30 < SiO2 /Al2O3 < 4.50
0.80 < Na2O/Al2O3< 1.60

Between activator and precursor:

10 < H2O/Na2O < 25

Where is possible the replacement of Na, by K or Li.

Considering the high content of iron oxide (Fe2O3) present in the fly ash, according to
Table 1 (10.2 wt %), was taken 30 wt% as a maximum addition of fly ash on metakaolin. The
iron element tends to replace the aluminum in the process of connecting the tetrahedral SiO42and it usually affects the mechanical strength [9].
Thus, and while respecting the given ranges of molar ratios, compositions were made by
adding 10 and 30%wt of FA, besides on a 100% metakaolin composition. In addition, all the
conditions used the HPMK and MSMK activating by the addition of Na and K activators. For
both activators used, the relation between them was 2:1 by weight (silicate: hydroxide), and
that for the hydroxides were prepared solutions 15 M (molar).
Following this methodology, samples (cones) were made for an empirical evaluation of
the refractory behavior and how different activators and addition of fly ash has direct
influence on this property of the geopolymer.

3. Results and discussion

Table 1 and 2 present the results of chemical and mineralogical analysis of the
precursors used, being that, the characters + (Table 2) represents a quantitative analysis of
the results found by X-ray diffraction.

Table 1 Chemical analysis of precursors of the geopolymeric reaction - * supplier - ** X-ray

fluorescence
Raw materials (wt%)

SiO2

Al2O3

Fe2O3

Na2O

K2O

TiO2

CaO

MgO

LOI

HPMK*

56,2

34,8

2,2

0,0

1,9

1,3

0,0

0,2

2,6

MSMK**

49,7

35,0

0,5

0,1

1,5

0,0

0,1

0,2

2,98

FA**

55,3

19,8

10,2

0,0

2,3

1,0

1,3

0,7

2,75

Table 2 Mineralogical analysis of precursors of the geopolymeric reaction obtained by X-ray

diffraction
Raw materials (%)

Crystalline Phases

Amorphous

Quartz

Kaolinite

Muskovite

Hematite

HPMK

++++

++

++

MSMK

++++

+++

++

++++

FA

++++

+++

+++

In order to observe how the alkaline activator and the fly ash content affect the
geopolymer refractory behavior, samples (cones) of each composition were firing in a
Lindenberg Blue CF56724C furnace, whereas similar firing curves: heating rate of 5 C/min.,
landing time of 5 min. and cooling rate of 10 C/min.
Analyzing the results of the compositions with MSMK, activated with Na, it was found
that the temperature peak (taken as operating temperature) which the sample maintains the
structure without deformation was 1000C (Figure 1). The addition of 10 wt% of FA did not
caused any damage at this temperature (Figure 2). On the other hand, the addition of 30 wt%
of FA decreased this temperature to 800C (Figure 3).

Raw 700

800

900 1000

1100 (C)

Fig. 1. Effect of the temperature on the refractoriness of the composition 100% MSMK (Na)

Raw 700

800

900

1000

1100 (C)

Fig. 2. Effect of the temperature on the refractoriness of the composition 90% MSMK (Na)

Raw 700

800

900

1000

1100 (C)

Fig. 3. Effect of the temperature on the refractoriness of the composition 70% MSMK (Na)

For samples of compositions with HPMK (also activated with Na) it was observed that
the highest operating temperature was 900C (Figure 4), but the addition of 10 wt% of FA is
enough to decrease the temperature to 800C (Figure 5) and 30 wt% addition maintains this
behavior (Figure 6). This can be explained by the pronounced crystalline character of HPMK,
as shown on Table 2, and which impairs the alkaline activation.

Raw 700

800

900

1000

1100 (C)

Fig. 4. Effect of the temperature on the refractoriness of the composition 100% HPMK (Na)

Raw 700

800

900

1000

1100 (C)

Fig. 5. Effect of the temperature on the refractoriness of the composition 90% HPMK (Na)

Raw

700

800

900

1000

1100 (C)

Fig. 6. Effect of the temperature on the refractoriness of the composition 70% HPMK (Na)

For both compositions, MSMK and HPMK, activated with K the operating temperatures
found were higher compared to those activated with Na. These results are in accordance with
the literature [6]. Table 3 presents the operating temperature results for pure compositions,
10 wt% and 30 wt% FA addition. Figures 7 to 12 show the samples characteristics after heat
treatments.

Table 3 Operating temperatures of the compositions MSMK and HPMK activated with K.
Composition
MSMK
MSMK + 10 wt% FA
MSMK+ 30 wt% FA

Operating Temperature (C)

1400
1300
1300

HPMK
HPMK+ 10 wt% FA
HPMK+ 30 wt% FA

1300
1300
1300

Raw

1000

1300

1400

1500 (C)

Fig. 7. Effect of the temperature on the refractoriness of the composition 100% MSMK (K)

Raw 1000 1300 1400

1500 (C)

Fig. 8. Effect of the temperature on the refractoriness of the composition 90% MSMK (K)

Raw

1000

1300

1400

1500 (C)

Fig. 9. Effect of the temperature on the refractoriness of the composition 70% MSMK (K)

Raw

1000

1300

1400

1500 (C)

Fig. 10. Effect of the temperature on the refractoriness of the composition 100% HPMK (K)

Raw

1000

1300

1400

1500 (C)

Fig. 11. Effect of the temperature on the refractoriness of the composition 90% HPMK (K)

Raw

1000

1300

1400

1500 (C)

Fig. 12. Effect of the temperature on the refractoriness of the composition 70% HPMK (K)

Regarding to the geopolymers obtained with HPMK and activated with K, it was not
possible to observe an influence so prominent in the operating temperature by the addition of
the FA or the own crystalline metakaolin character as seen in the compositions of HPMK
activated with Na.
Taking as reference, the composition 90% MSMK activated with Na and MSMK 70%
activated with K, were evaluated by XRD in order to relate the operating temperature with the
melting point of the majority phase (Figures 13 and 14). In 90% MSMK activated with Na,
the majority phase was considered as Faujasite; its melting point is 1300C. Leucite, which
melting point is about 1690C, was considered the majority phase in MSMK 70% activated
with K.

Fig. 13. X-ray diffraction patterns of the composition 90 wt% MSMK activated with Na (crude left / fired at
900C right) shown the majority phases.
(

Sodium

Aluminum

Silicate

Hydrate;

Albite;

Faujasite;

Corundum;

Sodalite;

Sodium Aluminum Silicate)

Fig. 14. X-ray diffraction patterns of the composition 70 wt% MSMK activated with K (crude left/ fired at
1300C right) shown the majority phases.
( Leucite; Corundum)

4. Conclusions

The nature of the activator, Na or K, has a direct influence on the refractoriness of the
geopolymer materials as a function of the phases formed during the reaction.
The amorphous character of the precursor was also an important parameter of reaction
for the alkaline activation, activation being more prominent in the Na activated.
The operating temperature of the geopolymer materials are directly related to the
melting point temperature of the majority phases formed during the geopolymeric reaction.
The development of geopolymer materials for high temperature applications is
encouraging, particularly those activated by activators based K.

Acknowledgements

The authors gratefully acknowledge the financial support of the So Paulo Research
Foundation (FAPESP) and the Graduate Program on Materials Science and Engineer
(PPGCEM - UFSCar) for the current work.

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