Australian Journal of Basic and Applied Sciences, 7(5): 246-257, 2013

ISSN 1991-8178

Review on Current Geopolymer as a Coating Material

M.S. Siti Salwa, A.M. Mustafa Al Bakri, H. Kamarudin, C.M. Ruzaidi, M. Binhussain, S.Z.
Sharifah Zaliha
1
Center of Excellence Geopolymer and Green Technology (CEGeoGTech), School of Material
Engineering, University Malaysia Perlis (UniMAP), P.O Box 77, d/a Pejabat Pos Besar, 01000
Kangar, Perlis, Malaysia.
2
King Abdul Aziz City Science & Technology (KACST), P.O. Box 6086, Riyadh 11442, Kingdom of
Saudi Arabia

Abstract: A world towards the concept of sustainable development and environment with low
greenhouse gas emissions, zero waste and low energy consumption is an important endeavor.
Geopolymer is an aluminosilicate materials occurred by dissolve it in highly alkaline solution then
transform into tridimensional tecto-aluminosilicate materials. As an inorganic material, geopolymer
has a potential in fire resistant and protective coating for different surfaces including metal and
concrete due to their superior mechanical, chemical and thermal resistance properties. With an
additional engineering design, in curing and sintering temperature, Si:Al ratio as well as additives used
will improve the geopolymer coating properties. The present paper outlines briefly the potential of
geopolymer as a coating material to bring the world towards a better future with a reduced carbon
footprint.

Key words: geopolymer, coating

INTRODUCTION

The environmental concerns about the increasingly evident ecological consequences due to human activities
have come to worldwide attention. In the early and mid-1980s, Our Common Future popularized the concept of
sustainable development (Robinson, 2004; Brundtland, 1987). Researchers and industrialists have searched for
ways of making industrial processes more sustainable.
Industrial ecology is the most efficient way to achieve sustainable development (Blisset and Rowson, 2012)
by using the by-product generated in particular industrial processes which assimilate in other industrial
activities. As an example coal combustion in power plant produced fly ash as a by-product and the by-product is
assimilate in concrete industry (Mustafa et. al., 2012). This minimizes the overall material and energy
consumption as well as reducing the economic costs and environmental pollution.
Rapid development of a country increasingly the greenhouse gasses since a lot of the development use raw
materials that emit carbon dioxide, CO2 into our atmosphere. For example, in cement industry, the production of
one ton Ordinary Portland cement (OPC) requires the burning of large quantities of fuel as well as the
decomposition of limestone, resulting in nearly one ton of CO2 (Kong and Sanjayan, 2008). Cement plants have
been reported to emit up to 1.5 billion tons of CO2 into the atmosphere annually (Malhotra, 2002). Therefore,
the search for an alternative binder or new material to achieve the concept of sustainable development as to
bring no harm to the environment is an important endeavor.
There are several different group of fire proof material including cementitious materials, intumescent
paints, fibrous materials, etc (Temuujin et. al., 2011). Among these materials, cementitious materials as an
inorganic material and intumescent sodium silicate based paint are both commonly used. Generally,
cementitious materials are durable, wear resistant, inexpensive and do not combust when exposed to fire as its
coating is thick and heavy. But as they are made from OPC, they will lose strength and will adversely affected
by spalling when exposed to fire.
On the other hand, intumescent sodium silicate based paints can be used as thin coatings as its light,
aesthetic and smooth. But they are more expensive and often require extensive surface preparations. It also has
poor water resistance, low fire rating and may combine with CO2 to revert back to its original constituents of
silica dioxide, SiO2 and sodium carbonate, Na2CO3 (Horacek, 2000).
Na2Si2O5 + CO2 Na2CO3 + 2SiO2 (1)

Due to environmental concerns, geopolymer as the green material with many exceptional properties
including impressive fire resistance, capacity to encapsulate hazardous waste and inexpensive (Davidovits,

Corresponding Author: M.S. Siti Salwa, Center of Excellence Geopolymer and Green Technology (CEGeoGTech),
School of Material Engineering, University Malaysia Perlis (UniMAP), P.O Box 77, d/a
Pejabat Pos Besar, 01000 Kangar, Perlis, Malaysia.
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2008) is in great research to fully utilize its usage which as a coating material. Besides, it can also improve the
material or object properties such as corrosion resistance, wear, strength as well as preserving the environment.

Processing of Geopolymer Coating:

In geopolymer based production of its product, the emission of CO2 is lesser compared to other material
production such as the production of geopolymer industrial structure, railway sleepers (Johnson, 2008) and large
concrete columns (Hardjito et. al., 2005). As an inorganic polymer it do not preclude the presence of carbon
group. Furthermore it does not pose a threat to the environment throughout their life cycle of production,
refinement, application and disposal.
Geopolymer is one of the green materials that exhibit many exceptional properties such as high
compressive strength, low shrinkage, acid and fire resistant (Temuujin et. al., 2012) plus an ability to
immobilize toxic and radioactive materials (Xu et. al., 2005).
Mineral polymer is manifest in nature itself in great abundance. 55% of the volume of Earth’s crust is
composed of sialate-siloxo, Si-O-Al-O-Si-O and sialates, Si-O-Al-O. The process is based on the ability of the
aluminium ion, Al3+ to induce the crystallographic and chemical changes in a silica backbone. These mineral
polymers (Davidovits, 1976; Davidovits, 1982) which result from geochemistry or geosynthesis (Davidovits
1988) are latter called geopolymer in 1978 (Davidovits, 1979).
Since 1972, Davidovits, J., showed that the naturally occurring alumino-silicate materials with ceramic like
properties such as kaolinite are produced and transformed at low temperature into tridimensional tecto-
aluminosilicates in a very short time. This geochemistry rules the synthesis of zeolites and molecular sieves
(Barrer, 1957). The process yields nanocomposites (amorphous to semi-crystalline three-dimensional silico-
aluminate materials).
Geopolymerization process takes place when reactive aluminosilicate materials with less or no calcium
oxide, CaO component (such as metakaolin, fly ash) is rapidly dissolved in highly alkaline solutions, in the
presence of alkali hydroxide (sodium/potassium hydroxide, NaOH/KOH) and silicate solution
(sodium/potassium silicate, Na2SiO3/K2SiO3) to form free tetrahedral units, SiO4 and AlO4 in the solution. With
the development of reaction, water is gradually split out and these tetrahedral units are alternatively linked to
polymeric precursors (-SiO4-AlO4-, or –SiO4-AlO4-SiO4-, or –SiO4-AlO4-SiO4-SiO4-) by sharing oxygen atoms
forming amorphous geopolymeric products with a three-dimensional network structure (Zhang et. al., 2009).
The geopolymer are then cure at room temperature. The cation (potassium ions, K+ or sodium ions, Na+) present
in the framework cavities, balance the negative charge (Davidovits, 1994; Duxson et. al., 2007).
There have been several attempts on formation mechanism has been made since the invention of
geopolymers. However, Davidovits believed that the synthesis of geopolymer consist of three steps (Li and
Ding, 2001). The first step is dissolution of alumino-silicate under strong alkali solution which includes 8
pathways. In thermodynamic, different pathway can create different ion clusters that directly determine the final
properties of geopolymers. Thus, it is very important to understand the actual pathway in order to gain insight
into the mechanism of geopolymerization process. The second step is reorientation of free ion cluster and
followed by polycondensation process. Up until now, these studies are not done yet. This is because the forming
rate of geopolymer is very rapid. As a result, these three steps take place almost at the same time which makes
the kinetics of these steps inter-dependent.
According to Geopolymer Chemistry and Applications book (Davidovits, 2011), geopolymerization process
with metakaolin, MK-750 involves 3 phases. The first phase is alkaline depolymerization of the poly(siloxo)
layer of kaolinite. While the second phase involve the formation of the ortho-sialate (OH)3-Si-O-Al-(OH)3
molecule followed by polymerization (polycondensation) into higher oligomers and polymers.
The geopolymer reaction with NaOH or KOH is as follow. First step is the alkalination and formation of
tetravalent Al in the side group sialate -Si-O-Al-(OH)3-Na+. Then, the alkaline dissolution starts with the
attachment of the base hydroxide, OH- to the silicon atom, which is able to extend its valence sphere to the
penta-covalent state. The subsequent course of the reaction can be explained by the cleavage of the siloxane
oxygen in Si-O-Si through the transfer of the electron from Si to O, formation of the intermediate silanol, Si-OH
on the one hand, and basic siloxo, Si-O on the other hand.
Next step involve further formation of Si-OH groups and isolation of the ortho-sialate molecule, the
primary unit in geopolymerization. Follow by the reaction of the basic Si-O with the Na+ and formation of Si-O-
Na terminal bond. Then, the condensation between ortho-sialate molecules, reactive groups Si-ONa and
aluminium hydroxyl OH-Al, with production of NaOH, creation of cyclo-tri-sialate structure takes place,
whereby the alkali NaOH is liberated and reacts again and further polycondensation into Na-poly(sialate)
nepheline framework.
In the presence of waterglass (soluble Na-polysiloxonate) one gets condensation between di-siloxonate and
ortho-sialate-molecules, reactive groups Si-ONa, Si-OH and aluminium hydroxyl OH-Al-, creation of ortho-
sialate-disiloxo cyclic structure, whereby the alkali NaOH is liberated and reacts again. Finally, further

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polycondensation into Na-poly(sialate-disiloxo) albite framework with its typical feldspar crankshaft chain
structure takes place as shown in the Figure 1 above.
For chemical designation of geopolymers based on silico-aluminates, the term poly(sialate) that is an
abbreviation for silicon-oxo-aluminate has been proposed. Poly(sialates) are chain and ring polymers with Si4+
and Al3+ in 4-fold coordination with oxygen and their general formula is

Mn[-(SiO-2)2-AlO2]n.wH2O (2)

Where
M = monovalent cation such as K+ or Na+
n = degree of polycondensation
z = 1,2,3 or >>3

Fig. 1: Polycondensation into Na-poly (sialate-disiloxo).

Si:Al = 1, Ortho-sialate Si:Al = 2, Ortho(sialate-siloxo)

Si:Al = 3, Ortho(sialate-disiloxo)

Fig. 2: Geopolymer Oligomer Molecules.

Chains and rings are formed and cross-linked together always through a sialate, Si-O-Al-O bridge. The
amorphous to semi-crystalline three dimensional silico-aluminate structures are illustrated in Figure 2.
Geopolymer is form through geochemical processes of geomolecules during genesis can be classified into
two major groups which is pure inorganic and organic containing synthetic anologues of naturally-occuring
macromolecules. As we know, geopolymer is proposed as pure inorganic materials but it could be extend to
include geomaterials with organic content. The ancient Egyptians used straw and riverine mud containing
organics (e.g humic materials) to manufacture construction components of remarkable strength and durability.

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Roman concretes also contained mud as a binding agent. Therefore, it should be note the existence of crosslink
between inorganic and organic species during geopolymerization (Kim et. al., 2006; Davidovits, 1993).
The materials of geopolymer are a source material from solid phase and liquid phase. From solid phase the
material itself should be high percentage of silicon,Si and aluminium,Al. This material can act as geopolymer
precursor if it can dissolve in an alkaline solution and geopolymerize. Metakaolin (Kamseu et. al., 2010)
produced by calcinations of kaolin at 7500C and fly ash (Wan Mastura et. al., 2013) which contain 40-60% of
SiO2 and 20-30% of AlO3 is produced by burning pulverized coal are both use for the production of
geopolymers. 16 natural Al-Si minerals have been studied by Xu and van Deventer (Xu and van Deventer,
2000) as the potential source for the production of geopolymers.
Geopolymeric material show significant potential for utilization in a number of areas, essentially as a
replacement for OPC and also as a relatively inexpensive yet heat resistant ceramic material (Provis et. al.,
2006). Other potential applications of geopolymers include stabilization/immobilization of hazardous wastes,
surface capping and stabilization of waste dumps, construction of low permeability base liner in landfills, water
control structures, and construction of heap leach pads.
In the mining sector, geopolymerisation due to fast setting and high early strength of the paste may be
considered in back-fill or cut-and-fill operations (Van Jaarsveld et. al., 2000; Komnitsas et. al., 2007).
Geopolymers can even find applications as biomaterials. They have previously been considered for implant
applications, where they have shown to be bioactive with low tendency of ion leakage (Jamstorp et. al., 2010;
Oudadesse et. al., 2007; Catauro et. al., 2010).
Besides, there are a lot of by-products produced by industry today in huge quatities in every country
including mining, metallurgical, municipal, construction and demolition that can also be utilize as a feedstock
for geopolymers, such as fly ash, blast furnace slag, bauxite residues and mine tailing. As an inorganic polymer
based on synthetic aluminosilicate (Davidovits, 1993) materials, geopolymer has a potential in fire resistant and
protective coating for different surfaces including metal (Temuujin et. al., 2010) due to their superior
mechanical, chemical and thermal resistance properties (Yong et. al., 2007).
Uncoated material or object does not have a coating applied or covered to the surface of the object. It is
generally not as smooth as coated material or object, more porous and tends to have lower fire resistance,
corrosion resistance and wettability compare to coat material or object. The uncoated material or object is
exposed directly to the harsh condition without any protection, e.g: fire, scratch, corrosion and bad weather.
Once the material or object is damaged (crack or corrode) it would be costly to repair thus shortens the service
life of the material or object.
However, coated materials or object is covered with a layer of coating material. This coating material
protects the material or object from exposed to the harsh condition. Thus, extend the life of the material or
object. In National University of Malaysia, Che Haron et. al. (2011) found that the 350-diamond-shaped insert
with simple grooves of coated carbide tools were superior to the uncoated carbide tools and their flank wear
grew smoothly. This research showed that coated material or object is better in its properties compared to
uncoated material or object.
Basically, coating is applied to the surface of an object or substrate to improve surface properties of the
substrate, such as appearance, adhesion, wettability, corrosion resistance, wear resistance, scratch and also its
thermal resistance. Application of the coating also allows the lifespan of existing infrastructure or product to be
lengthened as well as reducing the maintenance cost.
Balaguru et al. (2008) showed that the used of coating create a graffiti resistant surface by curing the matrix
of coating materials to a glassy texture and hence an organic paints do not adhere to the coated surface. These
coating used to prevent bad appearances or images of people vandalism while reducing the cost to clean up the
graffiti painted.
Coating can extend the service life of all polymer structure by improving the surface properties of surface
substrate such as ceramic and glass-ceramic coatings used in modern gas turbine (Han et. al., 2011), carbon
composite materials with silicon carbide coating in electrolysis (Zhang et. al., 2011), as well as silica coating
applied on polished ferrous (Le-Maguer et. al., ). These coating are applied to protect various hot zone
components from oxidation, hot corrosive, thermal and thermo-mechanical degradation and thus extend these
materials while maintaining or improving its mechanical and physical properties.
In other cases, in particular in marine concrete, the coating applied inhibits the intrusion of corrosive ions.
Thus, improve the anticorrosion properties of the marine concrete (Zhang et. al., 2010) while maintaining the
concrete properties.
While in Centre of Sustainable Resource Processing, CSRP conference, Rickard showed that geopolymers
are one possible solution to improve fire protection of an infrastructures and it is more economical since the raw
materials for geopolymers used are made from waste product (Rickard and van Riessen, 2008). This unique
properties can be applied in coating as it protect the material or object coated as well as used of geopolymer, an
inorganic material will lead towards sustainable environment. Figures below show an example of product with
and without coating with different material.

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(a) (b)

Fig. 3: Before (a) and after (b) coated with fluoropolymers in protection from seizing, galling, friction and
corrosion.

Fig. 4: Different type of coating material used.

There are several types of coatings that have been tried as surface protection materials such as acrylic,
polyurethane, epoxy, etc (Rodrigues et. al., 2000; Almusallam et. al., 2003; Medeiros and Helene, 2009) .
However, these organic coating usually covers on the material surface by physical absorption that makes it
caduceus. For a good coating application, the coating material need to be coat on the substrate by both physical
and chemical adsorption or bonding which will improve the material protection (Balaguru et. al., 2008).
In order to improve the adhesion of coating material to substrate, the use of an inorganic coating has been
proposed to substitute an organic coating. It is well known that geopolymer is an inorganic polymer or alkali
activated binders (Duxson et. al., 2007; Davidovits, 1994) has gained worldwide interests and its high
anticorrosion makes it a novel coating material. The coating formulation of geopolymer utilizes by-products that
would otherwise be disposed of in landfills at a growing cost and liability. Use of the by-product creates the
opportunity for carbon offset credits to further enhance profitability.
The geopolymer coating has valuable uses in municipal water systems, industrial applications,
transportation projects and petrochemical plants. The coating also offers an innovative, sustainable solution for
maintaining infrastructure in a manner that enhances public image and safety while reducing greenhouse
emissions.
Geopolymerization process occurred by synthesizing pozzolanic compounds or aluminosilicate source
materials such as fly ash, blast furnace slag, bauxite residues, and mine tailing with alkaline activator liquids
(sodium or potassium hydroxide) and sodium or potassium silicate. Then the mixture is subsequently mix and
cure at a moderate temperature. The geopolymerization process increase when the alkaline activator used
consists of soluble silicate; sodium or potassium silicate, rather than alkaline hydroxide alone (Palomo et. al.,
1999).
Numbers of research have been done in these past years by using geopolymer based such as metakaolin, fly
ash and blast furnace slag in coating (Temuujin et. al., 2012; Zhang et. al., 2010; Cheng and Chiu, 2003). In
2003, Cheng & Chiu fabricate a granulated blast furnace slag based geopolymer for fire resistant application.
The geopolymer panel made was exposed to a 11000 C flame, with the measured reverse-side temperature
reaching less than 3500 C after 35 min (Mustafa et. al., 2011). This research show that geopolymer based
material can withstand fire at high temperature thus allowing it to be made as coating material purpose by
altering its chemical composition in the reaction system.
Metakaolin ( China National Materials Group Corp.) and granulated blast furnace slag ( Zhujiaqiao cement
plant, Anhui, China) were used as coating material for concrete structures which exposed to marine
environment. These geopolymer used to inhibit the intrusion of corrosive ions (Zhang et. al., 2010). While
Temuujin used metakaolin prepared from Snobrite 65 kaolin from Unimin Corp. Australia (Cheng and Chiu,
2003) and fly ash from Collie thermal power station (Western Australia) (Temuujin et. al., 2010) as a
geopolymer based coating on metal substrates. The optimized coating formulation obtained show that these
geopolymer have very promising fire resistant characteristics. However, the adhesion properties of metakaolin
and fly ash based geopolymer to metal substrate depend on its chemical composition.

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In 2012, vermiculite which has a high dehydroxylation temperature up to 8000C were added at 10 mass
percent in fly ash based geopolymer coating as a fireproofing agent to geopolymer type composition to improve
its thermal resistant properties. For comparison, fine and coarse-ground vermiculite powders sample from South
Africa provided by Perlite and Vermiculite Factory (Perth, Western Australia) were prepared and added to the
coating formulation. The addition of the coarse-ground vermiculite to the fly ash show greater improvement of
fire resistant properties than the addition of the fine-ground vermiculite (Temuujin et. al., 2012).
Davidovits suggested that by changing Si:Al ratio, it is possible to regulate the properties of geopolymers .
Furthermore, by increasing the Si:Al ratio, the fire and heat resistant characteristics can be improved. The Si:Al
composition optimum for geopolymers prepared from metakaolin and fly ash observed by Temuujin were 2.5
and 3.5 respectively. While Cheng mentioned for silica oxide/aluminium oxide, SiO2/Al2O3 ratio in the range of
3.16-3.46, the geopolymer material showed an optimum compressive strength characteristic. However, as the
SiO2/Al2O3 ratio increase up to 3.85, the compressive strength decreased (Cheng and Chiu, 2003).
The chemical composition design is the basic key in gaining high compressive strength of geopolymer
coating. It includes the NaOH molarity, Na2SiO3/NaOH ratio, geopolymer/alkaline activator ratio and curing
temperature. Mustafa et. al. (2011) in his study revealed that a 12M NaOH solution and the combination of
geopolymer/alkaline activator with Na2SiO3/NaOH of 2.0 and 2.5 respectively produced the compressive
strength as high as 70 MPa (Mustafa et. al., 2012). This indicate that the chemical composition plays and
important role in obtaining desirable compressive strength as well as other properties.
There are a several coating method that can be used such as dipping (Temuujin et. al., 2009), spraying
(Temuujin et. al., 2010) and also painting (Balaguru et. al., 2008). However, by spraying a strong uniform
coating can be applied to a substrate and futher increase the adhesive strength. The ease with which geopolymer
can be applied onto substrate surfaces depend on the water content formulation. The water added into a starting
mixture is to increase the flow ability. But, it decreased the geopolymerisation reaction and did not give
beneficial thermal-resistant properties. For geopolymer coating preparation, it is important not to increase water
content instead it may be better to use additives such as plasticizers to increase the flow ability of the coating
material.
Another coating method that can be used is extrusion. For example, JFE Steel Corporation company [53]
managed to develop a high quality polyethylene, PE or polypropylene, PP coated steel pipe for the transmission
of gas, oil, water and other fluids with strong adhesion, excellent impact resistance, excellent bendability, easy
repair and highly resistant to corrosion from moisture and chemicals. JFE external coating pipe is produced by a
process of coating with a primer and PE or PP layer for small and medium diameter by extruded method and for
large diameter line pipe by the spiral wrapping method. The tensile strength pipes coated with PE reaches 19
MPa and for PP reaches 33 MPa .
Figures below show an example of pipe coating method by extrusion process (JFE Steel Corporation
company). The pipes coating involved two steps: First step is external coating (Figure 5, Figure 6) while the
second step involve internal coating (Figure 7).

Fig. 5: External coating.

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Fig. 6: External coating.

Fig. 7: Internal coating.

The testing method use in previous research was setting time test of fresh geopolymer paste by the Vicad
method (ASTM C191) (Zhang et. al., 2010). A Vicat needle was used to measure the geopolymer setting time.
Both initial setting time and final testing time were tested. The crystalline phases were identified from X-ray
diffraction (XRD) patterns obtained with a Bruker D8 Advance Diffractometer slipped with LynxEye detector
using Cu-Kα radiation. Diffraction patterns were collected from 100 to 800 2θ. The step size was 0.020 2θ with a
scan rate of 0.60 2θ per minute. Automated phase identification software (EVA 2, Bruker) was used to analyse
the diffraction patterns.
Geopolymer fracture surfaces were studied with a Zeiss EVO 40XVP scanning electron microscope with
EDS X-ray detector (Energy Dispersive Spectroscopy, Oxford Instrument). The adhesive strength of the coated
samples was measured with an Elcometer 106, adhesion tester according to ASTM D4541. Australian standard
1530.4 was used for measuring the heat insulating characteristics of the coatings. Using a custom made gas
heating rig, the standard time/temperature curve (Eq. 3) was followed as closely as possible.

T = 345 log10 (8t + 1) + 20 (3)

Where T device temperature in 0C at time t (min) form ignition of the heating rig.
Thermal expansion or shrinkage of geopolymer samples was measured with a DI-24 Adamel Lhomargy
dilatometer (Roissy En Brie, France). In order to make the sample hard enough for cutting with a diamond-
tipped blade, the cast sample were cured at 700C over night. Measurement was conducted according to ASTM
E831 over a temperature range of 200C-9000Cwith a heating rate of 50C/min. The average of the measurements
was used as the representative dilatometric curves, and all results lay within a 15% standard deviation. The
compressive strength of the geopolymer coating composition was measured by using an Instron-5500R testing
machine
Given the stone-like property of geopolymer, permeability was measured by Darcy method, which is
usually used to test the core in mining drill engineering. Sample of 3d aged was laid in pressure cabin and then
distilled water was pressed to permeate through. The surrounding pressure was 3 MPa higher than the driven
pressure to avoid water going through along the surface of sample. The permeated water over a period of time

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was recorded till the permeation was steady. Permeability was calculated according to the following formula
(API Production Department, 1988) :

k = 105.Q.µ.L/(A. Δp) (4)

in which:
k permeability coefficient (µm2);
Q velocity of permeated liquid (ml/s);
µ viscosity of permeated liquid (Pas);
L length of sample, fixed at 3.50 X 10-2m;
A sample cross-section area, 4.91 X 10-4m2;
Δp liquid pressure, set at 2 X 107 Pa.

Anticorrosion was mainly evaluated by the variation of compressive strength under three different curing
conditions at 20 ± 2 0C: air (RH = 90 ± 5%), seawater and dry-wet cycle. Dry-wet cycle was carried out
circulary by 12 h air curing and 12 h emerging in seawater. Concentrated Mocleodon artificial seawater ( 3-fold
concentration) was prepared as the reinforced corrosion medium. Specimens were tested on WHY-200 Auto
Compressive Resistant Tester ( Shanghai Hualong, China) at different curing ages.
The testing formulas for physical property tests such as water adsorption rate and volumetric density were
evaluated according to the Archimedes method. Water resistance of the coated samples were tested by a static
immersion test (Wang et. al., 2006) which comprises immersion of the coated samples in distilled water at 250C
and weighing after every 24 h after drying at 400C for 1 h. Mass change versus immersion time was evaluated
up to 72 h immersion.
For fire resistant tests, a 10mm thick geopolymer panel was exposed to an 11000C flame. The reverse-side
temperature of the panel was measured and recorded (Davidovits, 1999b). The thermogravimetric analyzer,
TGA measurements were performed on thermogravimetric analyzer/differential scanning calorimetry,
TGA/DSC1 Mettler Toledo equipment. Approximately, 20 mg of crushed powder was used for heating up to
1,000 0C using a heating rate and starting temperature at 100C/min and 500C, respectively. Measurements were
performed in air.
The relative effects of mechanical bonding and chemical bonding of substrate coated with geopolymer. The
substrates rods were embedded in the center of a mortar cylinder that was 38.1 mm tall and 57.2 mm in
diameter. The mortar was prepared from a mixture of water, Type I cement, and sand in the proportions
0.485:1.0:2.75, respectively, following the ASTM C109 guidelines. Fresh mortar was poured around the steel
rod to fill up the polypropylene container, and each container was tapped and vibrated to remove entrapped air
from the mortar prior to consolidation.
Prior to testing, all samples were kept in a 100% humidity environment at room temperature ( 200C ) and
cured up to 97 days. After curing, each cylinder was removed from its container and the bond strengths were
determined using the pin-pull testing configuration. The steel rod was pulled out of the mortar at a strain rate of
50mm per minute in displacement control. Both the applied load and the slip between the rod and mortar were
monitored with a built-in load cell and a built-in linear variable differential transformer (LVDT).
These testing used to prove and measure the ability of geopolymer materials to be used as a protective
coating on a different substrate.

Properties of Geopolymer Coating:

For coating applications, the adhesive force of the geopolymer based coating to substrate is very important
achieving the highest value in order to improve anticorrosion, fire and heat resistant, hardness as well as
extending the service life of the material. This is believed to be strongly influenced by the formulation of the
geopolymer (Temuujin et. al., 2009) the coating formulation is calculate by taking note the content and
composition of the amorphous part of the geopolymer used.
Scanning electron microscopy, SEM observations showed that the geopolymer bonding to steel was strong
and likely to be physical adhesion. Heating these geopolymer compositions to 10000C resulted in formation of
sodium aluminosilicate or nepheline (Temuujin et. al., 2009). The expansion of this geopolymer to temperature
provided a level of matching with the thermal expansion of the substrate resulting in maintenance of the
structural integrity of the coating. In order to achieve high adhesion strength between the substrate and coating
material, the bonding needs to be chemical adhesion.
Temuujin et, al. (2010) showed that the best adhesive strength observed was for high silica containing
composition (Si:Al = 3.5 ratio) which higher than 3.5 MPa and to achieve a greater fire insulating capacity the
coating thicknesses should be increase. The substrate used also affect the adhesion strength of geopolymer
coating material. The fly ash sample which is coated onto polished mild steel showed an adhesive strength of
2.7 MPa which is 0.5 MPa lower than non-polished mild steel substrate indicating that surface roughness

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influences adhesion strength. Microstructure evolution and thermal properties of the optimized coating
formulation show that they have very promising fire resistant characteristics.
Curing and sintering conditions also have a significant effect on the development mechanical strength in
most cementitious systems. Mustafa et, al. (2013) studied on fly ash from Manjung power station in Lumut,
Perak to produce as geopolymer coating paste. The geopolymer paste was sintered using temperature range from
6000C to 15000C showed an increase in strength up to 40 MPa after 7 days.
According to SEM observation (Figure 8), the geopolymer coating at 6000C show sever damaged of fly ash
particles while in the high temperature of sintering which is 15000C shows an interaction between fly ash fine
particles with the alkaline liquids. It is suggest that the coating represents a mixture of semi-reacted amorphous
glassy phase and fly ash microsphere (Temuujin et. al., 2011). Therefore, geopolymer materials is possible to be
use as a coating in high temperature application as it can withstand a maximum temperature of approximately
16000C (Cheng and Chiu, 2003).

(a) (b)

(c) (d)

Fig. 8: SEM image of geopolymer coating after sintering at certain temperature

(a) 600°C, (b) 900°C, (c) 1200°C, (d) 1500°C, [56]

Geopolymer produced with fly ash/alkaline activator ratios in the range of 1.4-2.3 shows high compressive
strengths, ranging from 42-52 MPa (Mustafa et. al., 2011). The geopolymer system is exposed to high
temperature (8000C) showed an increased in compressive strength up to 80 MPa. The strengths gain within 1-3
days. High compressive strength of 71.04 MPa is achieved for curing temperature of 600C. While the porosity or
permeability is less than 20% which is lower than OPC (Daniel et. al., 2007).
The shrinkage of the geopolymer coating material to concrete structure was controlled by using PP fiber
and self-prepared magnesium oxide, MgO expansion agent, later of which could produce a shrinkage
compensating effect (Zhang et. al., 2010). A previous research found that appropriate addition of PP fiber
decreased not only the compressive modulus but also the large shrinkage of geopolymers (Zhang et. al., 2009b).
In general, geopolymers intended for structural application with low Si:Al ratio, shrink with heating.
However, the geopolymer-type coatings with high Si:Al ratio, expand with heating (Provis et. al., 2009). In
order to apply geopolymer as an innovative coating material, solving the volume shrinkage is the key work.

Conclusion:
As conclusion, geopolymer based materials exhibit an excellent properties which can be used as a
protective coating material. This material also offers an innovative, sustainable solution for maintaining or
extending the service life of an infrastructure at a moderate cost while reducing greenhouse emissions. However,
there is lack of research on the geopolymer coating and it has not been popularize yet. It may still need
additional engineering properties such as the use of new additives, processing and sintering temperature as well
as geopolymer coating material in nanosize in order to improve properties of the coating material. On the other
hand, the use of geopolymer as an inorganic and green material will lead the world towards sustainable
environment with zero waste.

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 Aust. J. Basic & Appl. Sci., 7(5): 246-257, 2013

ACKNOWLEDGMENTS

This study was supported by Center of Excellence Geopolymer and Green Technology UniMAP and
School of Material Engineering, UniMAP. The authors of this research are very grateful to King Abdul Aziz
City Science and Technology (KACST) for the financial support of this study.

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