Journal of Non-Crystalline Solids 357 (2011) 1399–1404

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Journal of Non-Crystalline Solids

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / j n o n c r y s o l

Preparation and thermal properties of fire resistant metakaolin-based

geopolymer-type coatings
Jadambaa Temuujin a,b,⁎, William Rickard a, Melissa Lee a, Arie van Riessen a
a
Centre for Materials Research, Department of Imaging and Applied Physics, Curtin University of Technology, GPO Box U1987, Perth WA 6845 Australia
b
Institute of Chemistry and Chemical Technology, Mongolian Academy of Sciences, Ulaanbaatar 51, Mongolia

a r t i c l e i n f o a b s t r a c t

Article history: Geopolymer-type coatings prepared by using an industrially available sodium silicate solution (SiO2:
Received 24 June 2009 Na2O = 3.1) and metakaolin were applied to steel substrates. The coatings exhibited excellent adhesion to
Received in revised form 13 August 2010 steel substrates achieving greater than 3.5 MPa tensile stress. Dissolution of the coating in water after 72 h of
Available online 19 October 2010
static testing varied between 12.8 and 34.5 wt.% depending on the water content of initial formulations.
Coating formulations showed up to 3% thermal expansion after heating to 800 °C. Coatings maintained high
Keywords:
structural integrity with steel substrates when subjected to a heat treatment by a gas torch and formulations
Metakaolin;
Geopolymer;
calcined at 1000 °C for 1 h showed an X-ray amorphous structure.
Coating; © 2010 Elsevier B.V. All rights reserved.
Thermal properties

1. Introduction fire resistant properties than single cementitious or intumescent

coatings.
Steel is one of the most common engineering materials and thus its There exists a novel class of materials called geopolymer or alkali
fire resistant properties are very important. For instance, steel loses activated aluminosilicate. Geopolymer is a man made material with
50% of its room temperature yield stress at approximately 550 °C [1]. many exceptional properties including impressive fire resistance and
Fire proof materials are divided into different groups including capacity to encapsulate hazardous waste [3]. Geopolymer preparation
cementitious materials, intumescent paints, fibrous materials etc. Of involves mixing of the alkaline liquid (e.g. sodium hydroxide or
these materials cementitious materials and intumescent paints are sodium silicate) with an aluminosilicate such as metakaolin or fly ash
most commonly used. Cementitious materials are in general inorganic and subsequent curing at a moderate temperature.
and as such do not combust when exposed to fire. They are durable, Previously, we have shown that geopolymer prepared from
wear resistant and inexpensive but as they are made from Ordinary metakaolin, sodium silicate and Cabosil (very fine silica particles)
Portland cement (OPC), they will lose strength and will be adversely was promising as a thermal barrier coating on steel substrates [4]. The
affected by spalling when exposed to fire. Cementitious coatings also prepared material represents a composite comprising metakaolin
need to be thick, and thus heavy, if they are to provide adequate fire distributed within sodium silicate. It exhibited expansion, a charac-
protection. On the other hand intumescent paints are light, aesthetic, teristic of the intumescent material, and crystallizes to a zeolitic
smooth and can be used as thin coatings. But they are more expensive compound at 1000 °C in a manner similar to some geopolymer
and often require extensive surface preparation. One of the most materials. The partial dissolution of aluminium cations from meta-
commonly used intumescent coating is a sodium silicate based paint. kaolin being incorporated into the newly formed sodium silicate
However, it has poor water resistance, low fire rating and may results in good water resistance. However, preparation of the sodium
combine with carbon dioxide to revert back to its original constituents silicate from sodium hydroxide and fumed silica by continuous
of silicon dioxide and sodium carbonate [2]: mixing at elevated temperatures followed by resting the as prepared
sodium silicate for one day prior to use is inconvenient for practical
Na2 Si2 O5 + CO2 b= N Na2 CO3 + 2SiO2 ð1Þ applications. Moreover, using the fine grained fumed silica for
preparation of the sodium silicate solution requires a large amount
The authors of this paper consider that a combined coating made of water. The geopolymer which we were able to prepare contained a
from cementitious and intumescent materials would exhibit superior nominal water:cement weight ratio = 0.714 which is very high. Such
large amount of the water in a geopolymer formulation is usually
⁎ Corresponding author. Centre for Materials Research, Department of Imaging and
associated with large drying shrinkage, slow curing and low strength.
Applied Physics, Curtin University of Technology, GPO Box U1987, Perth WA 6845 Australia. For industrial preparation of geopolymer it is important to use
E-mail address: [email protected] (J. Temuujin). commercially available raw materials. The aim of the present research

0022-3093/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2010.09.063
1400 J. Temuujin et al. / Journal of Non-Crystalline Solids 357 (2011) 1399–1404

is to prepare coatings on metal from commercially available materials

and elucidate its fire and water proofing behaviour and compare its
properties with those prepared by using silica fume and sodium
hydroxide. Sodium silicate solution from Coogee Chemical Pty Ltd.
(Western Australia) with SiO2:Na2O = 3.1 was used as an industrially
available precursor. In our previous work we suggested that coating
compositions be processed with less aluminium (higher Si:Al) which
limits forming of a cross linked aluminosilicate geopolymer structure
throughout the whole sample. Therefore in this paper we have
adopted the term “geopolymer-type composition” rather than
“geopolymer composition”.

2. Experimental procedures

2.1. Raw materials

The starting materials used to make the geopolymer-type compo-

Fig. 1. XRD patterns of the metakaolin precursor and geopolymer-like compositions.
sition were: metakaolin prepared from Snobrite 65 kaolin from Unimin
Corp. (Australia), sodium silicate N42 with SiO2:Na2O = 3.1 and density
1.42 g/cm3 from Coogee Chemicals, sodium hydroxide pellets with
analytical purity and de-ionised water. According to the supplier's data 2.2. Characterisation
the viscosity of sodium silicate is 550 centipoise and water content 60.5%
w/w. Metakaolin was prepared by calcining the Snobrite 65 kaolin at Crystalline phases were identified from X-ray diffraction patterns
750 °C for 24 h. The chemical composition of the kaolin as measured by (XRD) obtained with a Bruker D8 Advance diffractometer operated at
XRF is as follows (wt.%): SiO2 46.36, Al2O3 37.6, LOI 13.5, Fe2O3 0.94, TiO2 40 kV and 40 mA using Cu-Kα radiation. Diffraction patterns were
0.8, MgO 0.24, K2O 0.22, CaO 0.2, Na2O 0.13, and SO3 0.07. collected from 5 to 80° 2θ. The step size was 0.02° 2θ with a scan rate
From previous work an optimal geopolymer-type composition was of 0.6° 2θ per minute.
selected that comprised Si:Al = 2.5 and Na:Al = 1. In order to elucidate Thermal expansion behaviour of the geopolymers type material was
the influence of the water:cement weight ratio on properties of the measured using a DI-24 Adamel Lhomargy dilatometer. The measure-
coatings on metal, we prepared 3 different water:cement compositions. ments were conducted over the range of 20–900 °C with a heating rate
Free water was added to the starting mixture to adjust the water: of 5 °C/min. A pyros 56 standard was used to calibrate the measure-
cement weight ratio. With the current starting mixture the calculated ments. The average of 3 measurements is presented as an expansion
water:cement ratio could not be reduced below 0.41. In principle it is versus temperature curve. The average of the 3 measurements lay
possible to reduce the water:cement ratio below this value if sodium within a 15% standard deviation. Sample MK-0.5 was too soft to obtain
silicate with a lower water content is used. Compositions were denoted thermal expansion data due to inadequate curing.
as MK-n, where n is the water:cement ratio of the mixture. Table 1 Coated samples were subjected to a direct flame from a gas torch
shows the composition of the starting mixtures. (flame temperature approximately 1100–1200 °C) for 30 min in order
Weighed raw materials were placed in a 300 ml plastic container to determine their high temperature performance and phase stability.
and mixed followed by de-foaming in a high speed centrifugal Thinky Cylindrical samples were subjected to 1000 °C for 1 h in order to
mixer for 5 min and 30 s, respectively. Mixing and de-foaming speeds investigate changes in the structure of the bulk samples.
were 1400 rpm and 2100 rpm, respectively. Consistency of the MK-0.5 Electron micrographs of both cylindrical samples (bulk) and coatings
mixture was more like water with a low viscosity, while MK-0.41 was exposed to the gas torch were obtained with a Zeiss EVO 40XVP
more viscous and suitable for dip coating. The consistency of the MK- scanning electron microscope. The adhesive strength of the coated
0.45 mixture was somewhere between the MK-0.41 and MK-0.5 samples was measured with an Elcometer 106, adhesion tester
mixtures. Mild steel plates with approximate dimensions of 5 × 6 cm according to ASTM D4541.
were coated by dipping into the geopolymer mixture. The steel plates
were prepared by cleaning with detergent followed by de-ionised water
and acetone. The dip-coated metal plates were placed in Petri dishes
which were in turn sealed inside plastic snap lock bags and cured at
70 °C for 24 h. Because of the different viscosities of the mixtures, the
thicknesses of the MK-0.41 coatings were greater than the MK-0.5
coatings. Coating thickness varied between 0.2 and 0.5 mm. In addition
to the coatings some of the geopolymers were cured in cylindrical
plastic moulds of 50 mm length and 25 mm diameter at 70 °C for 24 h.

Table 1
Composition of the starting mixtures.

Sodium silicate, Metakaolin, Sodium hydroxide pellet, Water,

wt.% wt.% wt.% wt.%

MK-0.41 70.24 28.43 0.89 0.42

MK-0.45 67.64 27.38 0.86 4.09
MK-0.50 64.56 26.13 0.82 8.47
Fig. 2. Weight change–time curves of the coated samples immersed in water.
 J. Temuujin et al. / Journal of Non-Crystalline Solids 357 (2011) 1399–1404 1401

Two days after curing at 70 °C the water resistance of the coated 3. Results and discussion
samples was assessed using a static immersion test [5] which comprises
immersion of the coated samples in distilled water at 25 °C and Preliminary examination of the coatings on the metal substrates
weighing every 24 h after drying at 40 °C for 1 h. Percentage weight after 24 h showed that curing and hardening were successful. Samples
change versus immersion time was evaluated up to 72 h immersion placed in plastic tubes were still soft after 24 h. Samples MK-0.41 and
(Eq. (2)). MK-0.45 were hard enough to be removed from their tubes after
2 weeks, while MK-0.5 remained soft. It was apparent that the high
water content of the bulk MK-0.5 sample prevented curing and
W2 −W1 hardening.
WC = × 100% ð2Þ
W1 For fire resistant coatings the high adhesion strength of the coating
to the substrate is essential if the coating is to perform its fire resistant
function. The adhesion strength of all three samples was more than
WC weight change 3.5 MPa. However, the actual adhesive strength could not be deter-
W1 weight before water immersion mined because the measurement range of the Elcometer is limited to
W2 weight after water immersion and drying 3.5 MPa. These values are in very good agreement with previous results
on adhesion strength of the metakaolin geopolymers to steel substrates
Weight calculations are based on just the geopolymer-type coating. [4,6].

Fig. 3. SEM micrographs of the MK-0.41 (a, c), MK-0.5 (b, d) and metakaolin (e).
1402 J. Temuujin et al. / Journal of Non-Crystalline Solids 357 (2011) 1399–1404

Fig. 1 shows XRD patterns of the metakaolin and cured geopolymer-

type samples. The XRD patterns of the metakaolin shows an amorphous
halo centred at about 23° 2θ while for the geopolymer-type samples the
halo shifts to about 26° 2θ which is typical of geopolymer [7]. The
broadness of the XRD halo of the geopolymer-type samples suggests a
mixture of unreacted metakaolin and geopolymer-type material.
Fig. 2 shows the water stability of the coated samples expressed as
weight change against time.
Although XRD patterns of the samples were almost identical their
solubility in water differed greatly. Increased dissolution of the
samples with increasing water:cement ratios clearly indicated that
the degree of geopolymerisation is dependent on water content of the
mixtures. The highest weight loss was observed for the MK-0.5
sample which reached 34.5% after 72 h immersed in water. Dissolu-
tion in water is indicative of non-fully condensed geopolymer and the
likelihood of the presence of sodium silicate. Even though MK-0.41
had the smallest weight change it is still higher than samples prepared
Fig. 4. Dilatometric curves of the MK-0.41 and MK-0.45 samples. (Bulk samples were
by using sodium hydroxide and fumed silica [4]. In other words, cured in sealed plastic tubes at 70 °C for 24 h).
formation of the condensed geopolymer structure depends also on the
source of the sodium silicate as well as the preparation technique.
crystallisation of zeolite or nepheline phases after calcination of well
Metakaolin powder and fracture surfaces of the MK-0.5, MK-0.41
cured geopolymer at 1000 °C [8]. Schmucker and MacKenzie, Barbosa
samples are shown in Fig. 3.
and MacKenzie reported that well cured polysialate siloxo geopolymer
The microstructure of MK-0.41 and MK-0.45 shows a matrix of
(SiO2:Al2O3 = 2:1) maintained its amorphous structure after heating to
dispersed platy metakaolin particles. It also appears that the MK-0.5
1200 °C [9,10]. Previous work by the current authors also found that for
sample contains fewer and smaller platy particles and a larger portion of
a coating composition of Si:Al = 2.5 and Na:Al= 1 prepared from
gel structure than MK-0.41. This is contrary to the water stability curves
metakaolin and synthetically prepared sodium silicate crystallizes to
(Fig. 3), which suggests that the MK-0.41 sample has a more condensed
nepheline after heating to 1000 °C [4]. Generally, the formation of
microstructure which should shows more gel structure albeit a large
nepheline will depend on alkali content of the mixture. The apparent
portion of the gel structure may represent sodium silicate gel.
inconsistencies observed from the different experiments probably arise
Thermal expansion curves of the MK-0.41 and MK-0.45 composi-
from different precursor materials, geopolymer composition and
tions are shown in Fig. 4. Both samples initially shrink then expand.
preparation procedures.
Shrinkage occurring for both samples up to 200 °C is most probably
Based on the water stability behaviour it was thought that the
related with dehydration of free or weakly bound water from the
dissolution of the aluminium cations into sodium silicate was a key
geopolymer. The higher shrinkage of the MK-0.45 sample is possibly
factor for the formation of the condensed structure and that high water
caused by the presence of a larger amount of weakly bound water
stability implied a stronger condensed structure as was observed in our
compared with MK-0.41.
previous research [4]. However, the present research indicates that
It is also apparent that both samples have almost identical
compositions with a different water stability show similar thermal
expansion curves which differ only by the temperature at which
behaviour. This suggests that the influence of the geopolymer
expansion starts. The consistent and large expansion up to 800 °C
condensed structure on the thermal behaviour is not as profound as
suggests an intumescent like expansion. Finally above 800 °C the
was previously thought.
sample starts to shrink and this is ascribed to a densification of the
Fig. 6 shows SEM micrographs of the MK-0.41 and MK-0.5 samples
structure possibly from sintering and viscous flow. The main features
pulled off the steel surfaces after thermal treatment with the gas torch
of the thermal expansion curves resemble curves from samples
for 30 min. A fine needle like structure was observed in the MK-0.5
prepared by using our own preparation of sodium silicate [4].
sample which, if crystalline, is below the detection limit of XRD. The
Both MK-0.41 and MK-0.45 suffered weight losses of 19.16% and
presence of the needles indicates that there is crystallisation occurring
22.56%, respectively after seven days post de-moulding in ambient
conditions. Thus almost all additional water in these compositions exists
as free or weakly bound water which we believe does not influence the
expansion of the samples observed in the dilatometry curves.
Steel coated samples subjected to thermal treatment by gas torch
show high structural integrity with no evidence of crack formation.
Maintaining structural integrity is an important and essential
requirement of the thermal coatings. Although the dilatometry curves
show an initial shrinkage of the samples with increase in temperature,
when coated on steel the geopolymer is obviously sufficiently flexible
to cater for the mismatch between itself and the steel.
Fig. 5 shows XRD patterns of the bulk samples calcined at 1000 °C
for 1 h and it is clear that even after high temperature calcining the
microstructure of the coating composition remains amorphous. What
is surprising is that centre of the amorphous halo has moved from
approximately 25° 2θ (Fig. 1) to 22° 2θ matching the signature of the
metakaolin. The width of the halo has also reduced to be almost the
same as the metakaolin halo. This suggests that the geopolymer-type
structure has broken down leaving mainly unreacted metakaolin.
Thermal evolution of metakaolin-based geopolymer is complex and Fig. 5. XRD patterns of the calcined samples and for comparison the 1000 °C calcined
various authors have presented different results. Duxson et al. observed metakaolin.
 J. Temuujin et al. / Journal of Non-Crystalline Solids 357 (2011) 1399–1404 1403

Fig. 6. SEM micrographs of the MK-0.41 (b and d) and MK-0.5 (a and c) samples after exposure to a gas torch for 30 min at approximately 1100 °C and then stripped from the metal
substrate.

from the glassy structure. Both samples show a highly porous glassy the final properties of the product. Controlling not only composition
microstructure. It is proposed that the highly porous microstructure is but also the chemistry of the precursor materials is essential for
generated by water release from the composition at low temperatures controlling the properties of the synthesised geopolymer. Even
followed by sintering and viscous flow at higher temperatures. Both though, the chemical composition of the sodium silicate prepared
processes, dehydration and formation of the porous microstructure, are from sodium hydroxide and fumed silica should be similar with that
desirable for thermally insulating material on the metal substrates. obtained from industrial manufacturers, apparently their silicate
Generally, the geopolymerisation process starts with dissolution of structure differs which impacts on the properties of the geopolymers.
solid particles into an alkaline solution followed by gelation and High water content in slurry will reduce the concentration of
polymerisation of added silicate solution with Al and Si complexes dissolved aluminium species and consequently also reduce gelation
and finally reorganisation and polymerisation and hardening [11,12]. and hardening of the geopolymer-type composition. Therefore, MK-
Except for the dissolution of the solid aluminosilicate source by 0.45 and MK-0.5 samples show less water resistance than the MK-
alkaline hydrolysis (consuming water) the gelation, reorganisation 0.41 sample. Southam et al. state that it is impossible to prepare a
and polymerisation and hardening release water [11]. This means sodium silicate solution by using sodium hydroxide and silica fume
there is excess water after dissolution of the aluminate and silicate with the same properties as an industrially available sodium silicate
species. The presence of excess water will inhibit polymerisation and source [13]. It is important to develop an understanding of why
hardening of the gels. Although geopolymer-type samples coated on different sources of sodium silicate result in varying geopolymer
the steel surfaces were cured and hardened, it is apparent that cross properties if the geopolymer field is to mature and grow. It is more
linking of the aluminate and silicate condensed structure did not than likely related to differences in the silicate species in solution as
occur thus leading to reduced water stability. mentioned earlier. Although it was difficult to prepare a thermal
The experimental results identified several aspects of varying coating material with high water stability, controlling and reducing
water content and utilising different starting materials for preparation the water in precursor materials may ultimately allow preparation of
of the fire resistant coatings: coatings with both high thermal and water stability.
– Metakaolin dissolved in sodium silicate prepared by mixing
4. Conclusions
sodium hydroxide and silica fume exhibits different geopolymer-
isation behaviours than geopolymers manufactured from com-
Geopolymer-type coatings prepared by using industrially available
mercially available sodium silicate solution.
sodium silicate show different thermal and water resistant properties
– The water content of a geopolymer formulation has considerable
than those prepared from synthetically prepared sodium silicate.
influence on the geopolymerisation reaction.
Using a geopolymer-type composition with a water:cement ratio of
The present research indicates that the type of precursor materials 0.41 shows improved water stability when compared with samples
used for the manufacture of geopolymer plays a very important role in with a water:cement ratio of 0.5 which lost 34% of its weight after 72 h
1404 J. Temuujin et al. / Journal of Non-Crystalline Solids 357 (2011) 1399–1404

static leaching in water. Even though the prepared geopolymer-type [2] H. Horacek, S. Pieh, Polym. Int. 49 (2000) 1106.
[3] J. Davidovits, Geopolymer, Chemistry and Applications, Institut Geopolymer, 3rd
coatings showed reduced water stability, their adhesion to metal printing, Saint-Quentin, France, p.585 (2008).
substrates and thermal resistance were excellent. [4] J. Temuujin, A. Minjigmaa, W. Rickard, M. Lee, I. Williams, A. van Riessen, Appl.
Clay Sci. 46 (2009) 265.
[5] Z. Wang, E. Han, W. Ke, Surf. Coat. Techn. 201 (2006) 1528.
Acknowledgements [6] J. Bell, M. Gordon, W. Kriven, Ceram. Eng. Sci. Proceed. 26 (2005) 407.
[7] Subaer, Influence of Aggregate on the Microstructure of Geopolymer. PhD
This project was carried out under the auspice and with the financial dissertation, Curtin University of Technology, (2004).
[8] P. Duxson, G.C. Lukey, J.S.J. van Deventer, J. N Cryst. Solid 353 (2007) 2186.
support of the Centre for Sustainable Resource Processing, which was [9] M. Schmucker, K.J.D. MacKenzie, Ceram. Int. 31 (2005) 4333.
established and supported under the Australian Government's Cooper- [10] V.F.F. Barbosa, K.J.D. MacKenzie, Mater. Lett. 57 (2003) 1477.
ative Research Centres Program. The authors wish to thank Coogee [11] P. Duxson, A. Fernandez-Jimenez, J.L. Provis, G.C. Lukey, A. Palomo, J.S.J. van
Deventer, J. Mater. Sci. 42 (2007) 2917.
Chemical Pty. for donating the sodium silicate.
[12] K. Komnitsas, D. Zaharaki, Miner. Eng. 20 (2007) 1261.
[13] D.C. Southam, K. Wright, W. van Bronswijk, International Fine Particles Research
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