Key Engineering Materials Vol.

660 (2015) pp 39-43 Submitted: 2015-05-12

© (2015) Trans Tech Publications, Switzerland Accepted: 2015-05-20
doi:10.4028/www.scientific.net/KEM.660.39 Online: 2015-08-26

Fire Resistant Properties of Geopolymers: A Review

Heah Cheng Yong1, a, Liew Yun Ming1, b, Mohd Mustafa Al Bakri Abdullah1, 2, c
and Kamarudin Hussin1, 2, d
1
Center of Excellence Geopolymer and Green Technology (CEGeoGTech), School of Materials
Engineering, Universiti Malaysia Perlis (UniMAP), 01000, P.O. Box 77, D/A Pejabat Pos Besar,
Kangar, Perlis, Malaysia.
2
Faculty of Engineering Technology, Universiti Malaysia Perlis (UniMAP), P.O. Box 77, D/A
Pejabat Pos Besar, Kangar, Perlis 01000, Malaysia.
a
cyheah@unimap.edu.my, bymliew@unimap.edu.my, cmustafa_albakri@unimap.edu.my,
d
vc@unimap.edu.my

Keywords: Geopolymers, inorganic, fire resistant, thermal properties

Abstract. This paper presents fire and thermal properties on geopolymer binders, composed of
metakaolin, slag and fly ash as precursor. Geopolymers are inorganic polymeric materials that are
believed being capable to resist heat, high temperature and fire. Based on the previous researches,
geopolymers offer a feasible alternative to fire resistance applications and with further deep studies,
it has great potential to be fabricated for engineering applications.

Introduction
Flame and fire resistant building materials are very important in every home and business over the
country. As result of various catastrophic fires involving organic plastic and polymers, it was found
that organic polymers are not fire and heat resistant. Only inorganic materials (minerals) can
provide fire and heat resistant [1]. Geopolymers are inorganic polymer materials with ceramic-like
structure and properties [2]. Geopolymers are well-known as having high mechanical properties,
low shrinkage, low permeability and good thermal properties [3-6]. For instance, geopolymers
rapidly hardens at room temperature (4 hours) and provides early compressive strength of
approximately 20 MPa. The 28-day strength of geopolymers would be in the range of 70 – 100 MPa
[7]. Besides, according to Davidovits [8], geopolymers are stable up to 1000 - 1200°C. Due to these
properties, geopolymers can be effectively applied in various fields of industry such as civil
engineering, automotive and aerospace, non-ferrous foundries and metallurgy, decoration and
building retrofits [9].

Terminology
Geopolymers are synthesized by the reaction between aluminosilicate sources and activator solution
(mixture of alkali solution and liquid waterglass). The process of geopolymers formation is called
geopolymerization process. The product yields polymeric Si-O-Al bonds [2] and has Al cations in
IV-fold coordination and tetrahedral position [10]. The SiO4 and AlO4 are tetrahedral linked by
sharing oxygen atoms. Cations such as Na+, K+ and Li+ are present in the framework cavities of
geopolymers to balance the negative charge of Al3+ [1-2]. The formation of geopolymers can be
schematized as shown in Fig. 1. (Si2O5, Al2O2)n denotes the aluminosilicate oxides with IV-fold
coordinated Al3+ [1].

Geopolymers for Fire Resistant Applications

In 1982, formation of geopolymer matrix composite (GEOPOLYCERAM) with alkaline resistant
inorganic reinforcements has produced non-inflammable, non-smoke and non toxic materials [2].
Geopolymer has been applied in thermoforming of glass (500−700°C) and casting of aluminium
(800°C). In 1990, geopolymer resins (GEOPOLYMITE) as high temperature tooling materials has

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40 Innovative Materials and Engineering Research

been firstly presented focusing on the chemical composition and physical properties of geopolymers
[8]. They have been used in building’s thermal insulation, furnace insulation, tooling, molding work
and etc. Geopolymer has also been used in building products as fire-resistant chip-board panels
which comprised of wooden core coated with geopolymer nanocomposite (SILIFACE Q) [1].

Fig. 1: Schematic diagram showing the reaction equation for geopolymer formation [1].

Collaboration works between Geopolymer Institute with Federal Aviation Administration

Technician Center and Rutgers the State University of New Jersey, USA, had started two projects,
which are, geo-composite and geo-structure. Geo-composite is fire resistant composite used for
aircraft and cabin interior applications, public transportation, military vehicles and offshore oil
platforms. On the other hand, geo-structure is applied in structural external repair and rehabilitation
for aging infrastructures and buildings [11]. In 1994, this geopolymer composite have been
employed in aviation applications. They are capable of eliminating cabin fire during the aircraft
accident compared to existing plastic materials that combust easily and emit flammable gas [12].
Geopolymer is also adopted in the Formula One car as thermal shield until today due to its
properties that can withstand vibration and heat (> 700°C) [12].

Fire and Thermal Properties of Geopolymers

In 1996, the fire response of geopolymers carbon fiber composites was firstly presented by Lyon et
al. [11] and compared with some organic polymer composites. The ignitibility, heat release and
smoke release (ASTM E-1354) of all tested samples were conducted in an oxygen consumption
calorimeter. Organic composites such as thermosets, advanced thermosets, phenolics and
engineering plastics ignited easily and released substantial heat and smoke. Responded differently,
geopolymer composites did not ignite and combust or even release heat or smoke under exposure to
extended heat flux. Besides, geopolymer composites have flame spread index of zero, suggesting
that the geopolymer composites did not propagate fire and would be an excellent fire barrier or fire
stop. This gives fire victims more time to escape.
After fire exposure, geopolymer matrix is white in color. Furthermore, geopolymer composites
retained 63% of its original flexural strength after exposure to severe fire exposure (800°C/
75kWm-2) for 60 minutes. The residual flexural strength was so much higher than other organic
polymer composites where in they only retained about less than 55% of the original strength even at
moderate fire conditions (25kWm-2 for 20 minutes) [11]. Lyon et al. [13] also observed the change
in microstructure of geopolymer resins when conducting the thermogravimetric analysis (TGA). At
room temperature, geopolymer is microcellular amorphous material. Strong, fused, glassy resin is
formed at above 850°C. Also, geopolymers is durable under UV light [14].
Compared to conventional organic polymers, glass, ceramics, cement or concrete, geopolymers
have attractive properties as being non-combustible, non-flammable and fire/heat resistant. Cheng
et al. [15] produced fire resistant geopolymers using metakaolin with addition of ground blast
furnace slag as filler. The fire resistant test was carried out using 10mm thick geopolymer panel
exposed to 1100°C flame and the reverse-side temperature was recorded. A good fire resistant
material is produced with reverse-side temperature of less than 350°C after 35 minutes (ASTM
 Key Engineering Materials Vol. 660 41

E119). He found that fire resistant of geopolymers was influenced greatly by the concentration of
KOH; where in the fire resistant properties of geopolymer was enhanced with increasing KOH
concentration. Increasing amount of metakaolin in geopolymer mixtures degraded the fire resistant
properties. No direct correlation can be deduced when varying the amount of sodium silicate added.
However, in general, fire resistant of geopolymer is better with decreasing sodium silicate content.
Lecomte et al. [5] reported high melting temperature of geopolymers around 1260°C suggesting
the excellent thermal stability of geopolymers. Barbosa & MacKenzie [16] stated that potassium
polysialate (K-PS) geopolymer retained its dimension stability even heated up to 1400°C for 1 hour.
On the contrary, potassium sialate disiloxo (K-PSDS) geopolymers became porous and friable on
heating above 1200°C. This suggested that the thermal behavior of geopolymers is significantly
affected by the Si/Al ratio [8]. Thermal analysis on sodium polysialate siloxo (Na-PSS) showed the
retention of structure dimensional stability upon heating to 1000°C and cooling. At > 800°C, slight
shrinkage occurred due to crystallization and/or densification within the geopolymer samples [17].
Barbosa & MacKenzie [17] produced geopolymer composites containing inorganic filler
powders such as crushed brick, stone, kaolinite, titanomagnetite ironsand, corundum and β-sialon.
In general, these geopolymer composites exhibited similar thermal expansion as unfilled
geopolymer, that is, dimensionally stable up to 800°C. The compatibility of these inorganic filler
with geopolymer matrix essentially influences the strength of geopolymer composites. Among all
inorganic fillers, composites added with corundum and β-sialon led to significant reduction in
strength when compared to unfilled geopolymers. However, all geopolymer composites showed
good thermal behavior. Even though high temperature caused thermal reaction of the filler itself, it
did not deteriorate the thermal properties but may contribute to strength enhancement of the
composites.
Besides, Rickard & van Riessen [18] carried out an experiment to study the effect of stimulated
fire exposure on the performance of solid and cellular structured fly ash geopolymers. The solid fly
ash geopolymers are prepared by using Si/Al ratio of 2.5 while the cellular structured fly ash
geopolymers are prepared by adding metallic aluminium to the geopolymer slurry. The result
showed that the cellular structured geopolymers samples possess improvement in their ability to
insulate heat. The fly ash geopolymers exhibited fire ratings of more than 90 minutes with
satisfactory water content and resistance to shrinkage cracking. However, solid fly ash geopolymers
showed better fire ratings than foamed geopolymers as result of higher water content.

Changes in Structure Upon heating

Rickard & van Riessen [18] have revealed the SEM images of three different types of fly ash
geopolymers before and after firing (Fig. 2). As shown in figure, they concluded that the firing of
fly ash geopolymers causes the sintering of the geopolymers paste which enhances the bonding
between geopolymers gel and un-reacted raw materials. However, among the three types of fly ash
geopolymers, Tarong fly ash geopolymers exhibited remarkable strength gains after fire exposure
and longer fire rating. This was due to the higher water content and good resistance to cracking.
X-ray diffraction (XRD) analysis of geopolymer shows typical amorphous characteristic of
diffuse halo peak at 2θ values at about 27° to 29° [19-20]. Upon heating in air at 1400°C for 1 hour,
changes in crystallinity of geopolymer were observed in K-PS and K-PSDS geopolymers. The K-PS
geopolymer crystallized to form mixture of leucite (KAlSi2O6) and kalsilite (KAlSiO4) at 1000°C.
No further change was reported on the mixture even up to 1400°C. Finally, the geopolymer melted
at 1400°C. For K-PSDS geopolymer, some crystalline component of kalsilite was seen at 1000°C,
but it converted to leucite at 1200°C. At 1400°C, the leucite crystalline component did not retained,
but reverted into fully amorphous forms [16]. This explained the reason that K-PS geopolymer are
showing better thermal stability than K-PSDS geopolymer.
Detailed changes in the XRD pattern of Na-PSS geopolymer was reported by Barbosa &
MacKenzie [17]. Differ from K-PS and K-PSDS reported above, Na-PSS remained amorphous at
temperature between 400-1100°C. Growth of mullite (Al2Si2O13) was seen at 1200°C and
corumdum (α-Al2O3) was appeared only at 1300°C. At 1300°C, the geopolymer melted. But, the
42 Innovative Materials and Engineering Research

authors stated that the formation of crystal phases was due to the unreacted residual starting
materials. No structure deformation on geopolymer was occurred.
Despite of various crystalline phases reported, it is believed that these formation of crystalline
phases that contributes to the good thermal and fire resistance at high temperature.

Fig. 2: SEM image of cellular structured geopolymers before (left images) and after firing (right
images). Top: Port Augusta, middle: Eraring and bottom: Tarong fly ash geopolymers [18].

Conclusion
This paper reviews the terminology of geopolymers, the application of geopolymers as fire resistant
materials, the fire and thermal properties of geopolymer materials and the characterization of
geopolymers when exposure to high temperature or fire. It was found that geopolymers showed
great potential to be fire resistant materials. Therefore, geopolymers can be fabricated into
engineering application in fire and thermal resistance areas to act as alternative fire resistant
materials for current market.

Acknowledgement
The authors gratefully thank to Center of Excellence Geopolymer and Green Technology
(CEGeoGTech) and School of Materials Engineering for providing expertise and full support.
 Key Engineering Materials Vol. 660 43

References
[1] J. Davidovits: J. Mater. Education Vol. 16 (1994), p. 91-139.
[2] J. Davidovits: J. Therm. Anal. Vol. 37 (1991), p. 1633 – 1656.
[3] P. Chindaprasirt, T. Chareerat and V. Sirivivatnanon: Cem. Concr. Compos. Vol. 29(3) (2007),
p. 224-229.
[4] S. Alonso and A. Palomo: Mater. Lett. Vol. 47(1-2) (2001), p. 55-62.
[5] I. Lecomte, M. Liegeois, A. Rulmont and R. Cloots: J. Mater. Res. Vol. 18 (2003), p. 2571-
2579.
[6] P. Duxson, J. L. Provis, G. C. Lukey, S. W. Mallicoat, W. M. Kriven and J. S. J. v. Deventer:
Colloids Surf. A Vol 269 (2005), p. 47 - 58.
[7] J. Davidovits: World Resour. Review Vol. 6 (1994), p. 263 - 278.
[8] M. Davidovics, J. Orlinski, J. Davidovits and Society of Manufacturing Engineers, in:
GEOPOLYMER: Ultra-high temperature tooling material for the manufacture of advanced
composites (Society of Manufacturing Engineers 1990).
[9] L. Zongjin, Z. Ding and Z. Yunsheng, in International Workshop on Sustainable Development
and Concrete Technology (2004).
[10] J. Davidovits, U.S. Patent 4349386 (1982).
[11] R.E. Lyon, U. Sorathia, P. N. Balaguru, A. Foden, J. Davidovits and M. Davidovics, in First
International Conference on Fiber Composites in Infrastructure (LCCI' 96) Tucson. (1996).
[12] J. Davidovits: in Geopolymer 2002 Conference (Geopolymer Institute, Saint-Quentin, France,
Melbourne, Australia 2002).
[13] Lyon, R.E., P. N. Balaguru, A. Foden, U. Sorathia, J. Davidovits and M. Davidovics: Fire and
Matrials Vol. 21 (1997), p. 67-73.
[14] S. Kurz, P. Balaguru, R. Lyon and J. Davidovits, in Second International Conference
Geopolymere'99. (1999).
[15] T.W. Cheng and J.P. Chiu: Miner. Eng. Vol. 16 (2003), p. 205 - 210.
[16] V.F.F. Barbosa and K.J.D. MacKenzie: Mater. Lett. Vol. 57 (2003), p. 1477-1482.
[17] V.F.F. Barbosa and K.J.D. MacKenzie: Mater. Res. Bull. Vol. 38 (2003), p. 319-331.
[18] W.D.A. Rickard and A. van Riessen: Cem. Concr. Compos. Vol. 48 (2014), p. 75-82.
[19] J. Davidovits: J. Mater. Education Vol. 16 (1994), p. 91-139.
[20] J. Davidovits, in Proceedings First International Conference (Geopolymer Institute, Saint-
Quentin, France 1994).
Innovative Materials and Engineering Research
10.4028/www.scientific.net/KEM.660

Fire Resistant Properties of Geopolymers: A Review

10.4028/www.scientific.net/KEM.660.39

DOI References
[20] J. Davidovits, in Proceedings First International Conference (Geopolymer Institute, SaintQuentin, France
1994).
10.1002/9780470310496.ch34
[19] J. Davidovits: J. Mater. Education Vol. 16 (1994), pp.91-139.
10.1109/te.1973.4320851
[18] W.D.A. Rickard and A. van Riessen: Cem. Concr. Compos. Vol. 48 (2014), pp.75-82.
10.1016/j.cemconcomp.2013.09.002
[17] V.F.F. Barbosa and K.J.D. MacKenzie: Mater. Res. Bull. Vol. 38 (2003), pp.319-331.
10.1016/s0025-5408(02)01022-x
[16] V.F.F. Barbosa and K.J.D. MacKenzie: Mater. Lett. Vol. 57 (2003), pp.1477-1482.
10.1016/s0167-577x(02)01009-1
[15] T.W. Cheng and J.P. Chiu: Miner. Eng. Vol. 16 (2003), pp.205-210.
10.1016/s0892-6875(03)00008-6
[14] S. Kurz, P. Balaguru, R. Lyon and J. Davidovits, in Second International Conference Geopolymere'99.
(1999).
10.1002/(sici)1099-1018(199703)21:2<67::aid-fam596>3.0.co;2-n
[13] Lyon, R.E., P. N. Balaguru, A. Foden, U. Sorathia, J. Davidovits and M. Davidovics: Fire and Matrials
Vol. 21 (1997), pp.67-73.
10.1002/(sici)1099-1018(199703)21:2<67::aid-fam596>3.0.co;2-n
[12] J. Davidovits: in Geopolymer 2002 Conference (Geopolymer Institute, Saint-Quentin, France,
Melbourne, Australia 2002).
10.1002/9780470310496.ch34
[11] R.E. Lyon, U. Sorathia, P. N. Balaguru, A. Foden, J. Davidovits and M. Davidovics, in First
International Conference on Fiber Composites in Infrastructure (LCCI' 96) Tucson. (1996).
10.1002/(sici)1099-1018(199703)21:2<67::aid-fam596>3.0.co;2-n
[10] J. Davidovits, U.S. Patent 4349386 (1982).
10.1787/888932690073
[9] L. Zongjin, Z. Ding and Z. Yunsheng, in International Workshop on Sustainable Development and
Concrete Technology (2004).
10.1002/9780470950067
[8] M. Davidovics, J. Orlinski, J. Davidovits and Society of Manufacturing Engineers, in: GEOPOLYMER:
Ultra-high temperature tooling material for the manufacture of advanced composites (Society of
Manufacturing Engineers 1990).
10.1016/0956-7143(90)90261-t
[7] J. Davidovits: World Resour. Review Vol. 6 (1994), pp.263-278.
10.1016/b978-0-12-386513-7.00018-7
[6] P. Duxson, J. L. Provis, G. C. Lukey, S. W. Mallicoat, W. M. Kriven and J. S. J. v. Deventer: Colloids
Surf. A Vol 269 (2005), pp.47-58.
10.1016/j.colsurfa.2005.06.060
[5] I. Lecomte, M. Liegeois, A. Rulmont and R. Cloots: J. Mater. Res. Vol. 18 (2003), p.25712579.
10.1557/jmr.2003.0360
[4] S. Alonso and A. Palomo: Mater. Lett. Vol. 47(1-2) (2001), pp.55-62.
10.1016/s0167-577x(00)00212-3
[3] P. Chindaprasirt, T. Chareerat and V. Sirivivatnanon: Cem. Concr. Compos. Vol. 29(3) (2007), pp.224-
229.
10.1016/j.cemconcomp.2006.11.002
[2] J. Davidovits: J. Therm. Anal. Vol. 37 (1991), pp.1633-1656.
10.1007/bf01912193
[1] J. Davidovits: J. Mater. Education Vol. 16 (1994), pp.91-139.
10.1109/te.1973.4320851