Applied Clay Science 67–68 (2012) 57–60

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Applied Clay Science

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Potential application of geopolymers as protection coatings for marine concrete III.

Field experiment
Zuhua Zhang a, b,⁎, Xiao Yao b, Hao Wang a
a
Faculty of Engineering and Surveying, University of Southern Queensland, Toowoomba, QLD, 4350, Australia
b
College of Materials Science and Engineering, Nanjing University of Technology, Nanjing, 210009, China

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

Article history: Previous studies have shown a high potential of using geopolymers as new inorganic coatings in protecting
Received 19 May 2011 marine concrete. This article reports the results of the experiment on field application. Geopolymer coatings
Received in revised form 27 April 2012 were in-situ applied on the surfaces of concrete accropodes along the coast. It was observed that the geo-
Accepted 26 May 2012
polymer coatings set within 4 hours, bound strongly with concrete and were able to resist the wave shock
Available online 30 August 2012
in the first tide rise. There was a modicum of calcite detected by X-ray diffraction (XRD) but no sulphate
Keywords:
was found in the coatings within 6 months. One issue raised during in-situ application is the large shrinkage
Marine concrete of the geopolymer paste under ambient condition. Micro-cracks on the surfaces were observed after 7 days
Geopolymer although the MgO-based expansion agent and polypropylene (PP) fibers were added to withstand the shrink-
Coating age. The humidity of the atmosphere and the thickness of the coating layer are the two significant factors af-
Field experiment fecting the integrity of coatings. It was noted that the coating with a thickness of 5 mm at the tidal area,
Integrity where contact with seawater periodically, exhibited the best integrity. To solve the problem of large shrink-
age, it is recommended to use suitable aggregates in coating paste and to develop appropriate shrinkage re-
ducing agents together with careful curing procedures.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction for outside aggressive mediums. These corrosion processes reduce

The concrete structures exposed to aggressive marine environ-
ment, especially the steel reinforced structures, readily deteriorate
with time. This is because the cement hydration products and the
reinforced steel bar in concrete react quickly with aggressive
mediums. The mechanisms are mainly due to the carbonation of the
cement hydration products Ca(OH)2 in wet environment with the
presence of Cl −, Mg 2+ and SO42− ions. The carbonation products
CaCO3 may block the capillary pores at the beginning; however, it
can be further dissolved when contacting with water. Consequently,
the pores allow more corrosive ions to move in and meanwhile the
decreased alkalinity of cement matrix due to the loss of Ca(OH)2 fur-
ther increases the potential of chloride corrosion. Chloride ion is one
of most dangerous ions for the reinforced concrete. It acts as a catalyst
to destroy the passive layer on steel and leads to a continuous corro-
sion once the pH of the pore water in concrete decreases to a critical
level. Besides, the reactions between the magnesium and sulfate ions
with the cement hydration products form expansive products and
further cause micro-cracks, which become the ingression channels
⁎ Corresponding author at: Faculty of Engineering and Surveying, University of
Southern Queensland, Toowoomba, QLD, 4350, Australia.
E-mail addresses: zuhuazhang@sina.cn (Z. Zhang), htm@njut.edu.cn (X. Yao),
Hao.Wang@usq.edu.au (H. Wang).
the life of concretes substantially.
Surface protection is applied to concrete structures to extend their
service life. Organic coatings, such as polyurethane coating, acrylic
coating, epoxy resin coating and chlorinated rubber coating, have
been applied on the surface of structures exposed to marine environ-
ment (Medeiros and Helene, 2009; Rodrigues et al., 2000). However,
since the aging under sunshine condition and the chemical and phys-
ical impacts of sea wave, the durability of the organic coatings is
doubtful. Using inorganic polymers, known as ‘geopolymer’, as pro-
tective coating materials may be an alternative choice. Geopolymers
are a family of alkali-activated cements with excellent resistance to
sulfate and seawater attack (Bakharev, 2005; Fernández-Jiménez
and Palomo, 2009). Geopolymer concretes exhibit much lower chlo-
ride permeability than ordinary Portland cement (OPC) concrete
(Bernal et al., 2011). Moreover, the presence of chloride in geo-
polymer matrix does not seem to affect the strength of concrete in
the long term (Makaratat et al., 2011; Rattanasak et al., 2011). It
means that the geopolymer concretes can keep the integrity even
the diffused chloride ions reach a certain concentration.
The possibility of using geopolymer as a novel coating material for
protecting marine concretes has been studied recently (Zhang et al.,
2010a, 2010b). It was found that the setting time of metakaolin-based
geopolymer coating can be adjusted by adding slag at an amount
accordingly to experiment temperature. The adhesion of geopolymer
coating to cement mortar substrate was appreciated. The shrinkage

0169-1317/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2012.05.008
58 Z. Zhang et al. / Applied Clay Science 67–68 (2012) 57–60

could be controlled by using MgO-based expansion agent and polypro- a

pylene (PP) fibers. However, since the experiments were performed at
the laboratory condition (Relative humidity= 90 ± 5%, 20± 2 °C), it
was difficult to conclude that the investigated geopolymer systems
were capable of providing a sustainable anticorrosion coating for con-
cretes exposed to natural marine environment. The primary purpose
of this technical paper is to update the research progress and to report
the results from the field experiment.

2. Experimental programs

2.1. Field location

The field experiment was performed on Shanghai Jinshan coast

(Hangzhou Bay, N30.705239, E121.334724). The large temperature
change between summer (up to 38 °C) and winter (low to −10 °C)
is the reason to select this location for examining the weatherability
of the coating. The field experiment started from 20th August 2010
(middle of summer) and the observation lasted for 6 months till
20th February 2011 (middle of winter). During this period, the ob- b
served temperature varied from 38 °C (highest in summer) to − 4 °C
(lowest in winter). A longer observation will be performed after this
stage when more field information is obtained and taken into consid-
eration of geopolymer formulation and coating procedures.
Three accropodes on the coast were chosen as the concrete sub-
strates. The concrete accropodes are placed in the tide zone to absorb
the wave energy, therefore to reduce the impact of wave on seawall
(Fig. 1(a)). The deterioration of accropods is very fast. Fig. 1(b)
shows the damaged accropods after being in service for only
6 years. Fig. 1(c) shows the characteristics of the three selected sur-
faces (denoted as SI, SII and SIII respectively): SI does not contact
with seawater while SII and SIII are immersed in seawater periodically.
The difference is that SII is back to the wave shock while SIII is face to
the wave shock.

2.2. Preparation of geopolymer coating

Table 1 provides the composition of the geopolymer coating. The

chemical composition of metakaolin, slag and sodium-based activator c
solution and the characteristics of MgO and PP were reported previ-
ously (Zhang et al., 2010a). The metakaolin, slag and MgO expansion
agent were dry mixed in a cement paste mixer for 10 min at a low
speed and then the activator solution with well distributed PP fibers
was poured in and mixed together until homogeneous slurry was
achieved. This mixing procedure was developed to prevent the aggre-
SI: dry
gation of PP fibers (Zhang et al., 2010a).

2.3. Coating procedure and examination

SIII: face to wave
The coating work was performed in the afternoon of 20th August
2010, a cloudy and windy day. On the coast, the temperature was SII: back to wave
26 °C, the wind reached to Grade 7 (13.9–17.1 m/s) and the relative
humidity was ~ 65%. After ebb tide, surfaces SII and SIII were scrubbed
with a wire brush to remove the sea shells and the loose mortar and
allowed to naturally dry for 30 min. The geopolymer slurry was man-
ually coated on SI, SII and SIII to a thickness of 3 mm, 3 mm and 5 mm
respectively with a putty brush. After the initial setting (about
30 min), the coatings were covered with wet straw mats. It was Fig. 1. Field experiment location (a), the deteriorated accropodes (b), and the surfaces
noted the final setting time under natural marine condition was with- to be coated (c).
in 4 h, which is shorter than the half tidal cycle (6 h). After being so-
lidified for two tidal cycles (24 h), the straw mats were removed to Table 1
allow coatings to be hardened under ambient condition. Composition of geopolymer coating.

The coatings were daily observed during the first month to record Metakaolin Slag Activator PP fiber MgO
the change in appearance. To examine the possible phase change in
mass% 42.97 7.52 47.17 0.39 0.95
the hardened coatings due to the contact with seawater, XRD was
 Z. Zhang et al. / Applied Clay Science 67–68 (2012) 57–60
carried out. The sampling and testing procedures for XRD were de-
scribed elsewhere (Zhang et al., 2010b).
3. Results and discussion
Fig. 2 shows the appearance of geopolymer coatings on SI, SII and SIII
at different ages. The coatings bound with concrete substrates very well
(Fig. 3a), although they have been exposed 6 h of wave shocking on SII
and SIII in the first 12 h. The color change with time at early age and the
different shrinkage properties were two notable phenomena. After
being solidified for 24 h, the color of the coatings changed from soil-
red to azury, a typical color that usually appears in the product of alkali
activated slag at early age, and then gradually turned back to the origi-
nal soil-red after being exposed in the marine condition for 7 d. There
was no notable color change afterwards. The most concerned property
is the integrity of the coatings under natural marine environment. It
was observed that the coating on SI (Fig. 3b) exhibited the highest
shrinkage, and a few of micro-cracks appeared on the edges after
24 h. This is because of the fast loss of water under the windy condition
(Lin and Ran, 2010) and may also partially be due to the chemical
shrinkage of geopolymer binder (Zhang et al., 2010a, 2010b). Although
the coating on SII (Fig. 3c) immersed in seawater for 12 h in the first
24 h, it still had shrinkage, which lead to the micro-cracks (the white
line indicated in Fig. 3c (left)). The coating on SIII had the best integrity
and no micro-crack was found in the first 24 h. However, after 7 d, a few
micro-cracks appeared on the coating but the size and concentration
were much smaller than those which appeared on SI and SII.
Fig. 3 shows a piece of 28 d-aged coating chip, which was forcedly
broken off from SIII. The coating chips being pounded down always
ripped off some concrete substrate, indicating that the bonding inter-
face was stronger than the substrate. Fig. 4 presents the XRD patterns
of the 28 and 180 d-aged coatings on SIII. Calcite was detectable in
both 28 d and 180 d products. However, sulphate was not found,
a b
24 h 180 d
c d
24 h 180 d
10 mm
Fig. 2. Geopolymer coatings solidified for 24 h and aged 180 d: a whole view on accropods (a); cracks to micro-cracks appeared on coating surfaces on SI (b), SII (c) and SIII (d).
Arrows point to micro-cracks.
59
PP fibres
Geopolymer Concrete
coating substrate
Fig. 3. Geopolymer coating forcedly broken off with cement substrate bound together.
The cracked chips are linked by PP fibres.
maybe due to the quantity is below the testing limitation of XRD.
From literatures, the magnesium and sulphate ions have been ob-
served in the fly-ash based geopolymer matrix when the specimens
immersed in seawater, although theses ions seem to have no signifi-
cant influence on the mechanical strength (Fernández-Jiménez and
Palomo, 2009). It is reported that the alkali activated slag/metakaolin
blends possess faster carbonation when more metakaolin is used
(Bernal et al., 2010). In this study, however, it should be noted that
the slag used in this system is 12 wt.% of the total solid content,
much less than those alkali activated slag or slag/metakaolin systems,
where the slag content is more than 80 wt.% (Bernal et al., 2010). In
return very limited amount of calcite silicate hydrates (C–S–H) was
formed. Therefore, the extremely slow ingression of ions and carbon-
ation are attributed to the compact structure of the coating and the
less C–S–H, which is one possible ingredient that may process
24 h 180 d
10 mm
24 h 180 d
10 mm
60 Z. Zhang et al. / Applied Clay Science 67–68 (2012) 57–60
α -Quartz
kaolinite
calcite
180 d
28 d
10 20 30 40 50 60 70 80
2-theta (degree)
Fig. 4. XRD patterns of the geopolymer coating on SIII at ages of 28 d and 180 d.
carbonation. The white solid product(s) appeared on coatings in the
early age (7 d) could be CaCO3 or a mixture of CaCO3 and Na2CO3. Al-
though there is no detectable Na2CO3 in the 28 d and 180 d products,
it cannot exclude the possibility that the formation of Na2CO3. Na2CO3
seems more possible because with the geopolymerization continuing,
the white product no longer appears as less sodium is available.
From the above observation it can be concluded that the geo-
polymer coating develops a high bonding strength within 6 h,
which is strong enough to resist the wave shock. The chemical stabil-
ity of the coating under marine condition is also sound. One potential
problem could be the water stability of fresh coating when contacts
with seawater (Temuujin et al., 2011). However, from the laboratory
and field experiments in this investigation, the geopolymer coatings
exhibited good water stability. The only issue noticed is shrinkage,
which causes a high tension stress on surface, resulting in micro-
cracks. Small cracks may not affect the bonding strength and the
chemical stability. However, cracks would allow the aggressive ions
to reach and corrode the concrete inside, and thus invalidate the func-
tion of geopolymer coating.
The humidity of the atmosphere and the thickness of coating layer
are the two factors that have significant impacts on the integrity of
geopolymer coating. The cracks appeared on SI are more and wider
than on SII. Since both coatings on SI and SII are of 3 mm thickness,
it is clear that periodical contact with seawater reduces the shrinkage
of coating. Applying geopolymer coating on the tidal concrete struc-
tures seems more preferred. The thickness factor can be seen by com-
paring the coatings on SII and SIII. Although they are suffered the same
tidal cycles, the thicker coating on SIII exhibits fewer cracks and better
integrity. It is concluded that increasing the thickness of the coating
from 3 mm to 5 mm is helpful in reducing the shrinkage of geo-
polymer coatings.
The addition of MgO-based expansion agent and PP fibers can ef-
fectively reduce the shrinkage of geopolymer paste at high humidity
conditions, reported at laboratory condition with RH = 90 ± 5%
(Zhang et al., 2010a). However, this method is less effective in con-
trolling shrinkage of geopolymer coating under natural marine condi-
tion. The first reason lies on the chemical shrinkage nature of
geopolymer binder, particularly for metakaolin-based geopolymer,
which requires a much higher liquid/solid ratio to achieve good
workability. The second reason is that the high speed wind on coast
accelerates the water evaporation during solidifying and causes a se-
rious shrinkage at plastic stage. The third reason is that the coating is
usually a relatively thin layer. The fast water loss of thin layer contrib-
utes to the dry shrinkage after hardening. Several remedies may be
helpful to solve the problem. One is using sand or other aggregates
to reduce the binder content in coating. It has been noted that a
higher sand/binder ratio results in low shrinkage (Vasconcelos et al.,
2011). Spraying suitable shrinkage reducing agents (moisturizers)
on the surface of coating or using viscosity modifying agents to re-
duce water evaporation may also work (Lin and Ran, 2010). However,
those commercial agents are only reported workable for normal con-
crete. Very limited information about geopolymer additives has been
disclosed yet. Further investigations are needed in both the coating
composition design and the field application procedure.
4. Summary
A novel geopolymeric coating material has been proposed with the
aim of protecting the concrete structures exposed to marine environ-
ment. The systematical experiments from laboratory and field applica-
tion have demonstrated the coating possesses suitable setting time,
high bonding strength and excellent anti-corrosion properties. The
chemical stability under marine condition enables it to provide a sus-
tainable protection to concrete structures. The large shrinkage during
setting and hardening can be reduced by adding MgO-based expansion
agent and PP fibers but not satisfactory under natural marine condition.
Recommendations for solving this problem include: 1) to keep the coat-
ing thickness > 5 mm; 2) to apply the coating at tidal area, where the
humidity is relatively high and the deterioration of concrete is more se-
rious; 3) to add suitable aggregates in coating paste and/or to develop
appropriate shrinkage reducing agents; 4) to apply careful curing pro-
duces at early age, such as cover wind shields.
Acknowledgements
The authors acknowledge the support of the Graduates Research &
Innovation Program (CX098_126Z) of Jiangsu province, China, the
International Postgraduate Research Scholarship provided by the
Australia government and the Halok Pty Ltd Research Scholarship.
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