You are on page 1of 9

Magazine of Concrete Research Magazine of Concrete Research, 2017, 69(1), 46–54

http://dx.doi.org/10.1680/jmacr.16.00118
Volume 69 Issue 1
Paper 1600118
Early strength and durability of Received 26/02/2016; revised 04/10/2016; accepted 05/10/2016
Keywords: admixtures/cement/cementitious materials/
metakaolin-based geopolymer concrete
compressive strength/durability-related properties
Alanazi, Yang, Zhang and Gao
ICE Publishing: All rights reserved

Early strength and durability of


metakaolin-based geopolymer
concrete
Hani Alanazi Dalu Zhang
MSc Student, Department of Civil and Environmental Engineering, PhD Student, Department of Construction Engineering and Management,
North Dakota State University, Fargo, ND, USA North Dakota State University, Fargo, ND, USA
Mijia Yang Zhili (Jerry) Gao
Assistant Professor, Department of Civil and Environmental Engineering, Associate Professor, Department of Construction Engineering and
North Dakota State University, Fargo, ND, USA (corresponding author: Management, North Dakota State University, Fargo, ND, USA
Mijia.yang@ndsu.edu)

Approaches to improve the early strength of geopolymer mortar were studied in order to apply it to a fast-tack
concrete pavement repair. The effects of modifying the molar ratio of silicon dioxide/sodium oxide (SiO2/Na2O) of
the alkaline solution in a conventional geopolymer mixture and the addition of calcium aluminate cement and slag
were studied. The early strength measured in the experiments was at curing times of 8 and 24 h, which are typically
construction controlling times for pavement repair. It was found that a molar ratio of silicon dioxide/sodium oxide of
1·0 gave the shortest curing time and the highest early strength after 24 h. Adding calcium aluminate cement was
found to reduce the curing time, but decrease the early strength. Slag substitution helped workability, but reduced
the early strength at 8 and 24 h. Durability was also tested for the purpose of finding an economical pavement
repair solution. A freeze–thaw durability experiment of the suggested metakaolin-based geopolymer concrete was
conducted. It was found that a mix with a silicon dioxide/sodium oxide molar ratio of 1·0 produced higher durability
than a mix with a silicon dioxide/sodium oxide molar ratio of 1·4. The geopolymer concrete mix with slag showed
less weight loss than the other mixes.

Introduction Previous studies have reported that the properties of geopoly-


Traffic volume has increased tremendously in urban areas of mer concrete (Hardjito et al., 2004, 2005) such as the modulus
the USA over the last decade (Buch et al., 2008; Van Dam, of elasticity, Poisson’s ratio and tensile strength are similar to
2005), meaning that aged pavements are deteriorating more those of PCC, indicating compatibility between geopolymer
quickly than previously. More and more concrete pavements concrete and PCC. Furthermore, geopolymers possess low per-
thus need to be repaired, and accelerated pavement repair is meability, excellent anti-corrosion and effective bonding with
an urgent requirement. A survey of over 20 US states with a cement paste and mortar (Zhang et al., 2010). Geopolymer
climate similar to that of North Dakota (Yang et al., 2013) can also be implemented using the same equipment and prac-
revealed that 73·7% of states use accelerated pavement repairs tices adopted for PCC (Montes and Allouche, 2012). In
for Portland cement concrete (PCC) pavements. In addition, addition, geopolymer concrete has better durability than PCC
more than 40% of these states consider the time to open to (Ariffin et al., 2013; Reddy et al., 2012; Sanni and
traffic as the most important factor in selection of a repair Khadiranaikar, 2012). All these merits make geopolymers an
material. In typical accelerated rehabilitation strategies, excellent alternative to Portland cement.
materials should be able to harden and be open to traffic on
the same day and the minimum compressive strength required The term ‘geopolymer’ was first introduced by Davidovits
for open to traffic is usually around 20·7 MPa. (1988) to describe a family of mineral binders that could cure
in an alkaline solution. Any materials that are rich in silica
Portland cement concrete with an accelerator admixture, which and alumina, such as fly ash or metakaolin, can be used as
can gain sufficient strength to carry traffic load in less than geopolymer reactants. The geopolymerisation process involves
24 h and sometimes in 4 h, is usually used in these types of dissolution of the geopolymer reactants in a strong alkali sol-
applications (Buch et al., 2008; Van Dam, 2005). However, ution, yielding polymeric Si–O–Al–O bonds in amorphous
high early strength PCC has been found to lack durability form. The geopolymer forms very rapidly and is an excellent
(Fu and Larmie, 2005). candidate for early strength applications (Davidovits, 1999;

46
Downloaded by [ University Of Wollongong] on [08/01/17]. Copyright © ICE Publishing, all rights reserved.
Magazine of Concrete Research Early strength and durability of
Volume 69 Issue 1 metakaolin-based geopolymer concrete
Alanazi, Yang, Zhang and Gao

Kamarudin et al., 2011; Xu and van Deventer, 2000). up to 1400–1500°C. It is a commonly held view that finding
Metakaolin was adopted in the current study as the main an alternative to Portland cement is urgent.
alumina-silicate binder due to its high rate of dissolution in the
reactant solution and its homogenous properties across differ- Metakaolin geopolymer is a new type of binder that could be
ent manufacturers (Duxson et al., 2007; Gourley, 2003; used to replace cement-based pavement repair materials.
Kamarudin et al., 2011). Success in curing metakaolin geopolymer at ambient tempera-
ture and achieving improved strength and durability will facili-
Compared with other repair materials on the market, metakao- tate ‘green’ pavement repairs and provide a foundation for
lin geopolymer mortar has shown superior bond strength more sustainable infrastructure maintenance. When applied in
(Alanazi et al., 2016). However, it requires a curing time of practical applications, durability is as important as the early
more than 24 h and is not permitted for applications demand- strength of the material. This research tested freeze–thaw dura-
ing an early open to traffic. Therefore, more research is needed bility to serve as a starting point to find a quick-curing repair
in order to achieve a shorter curing time and higher early material for concrete with adequate early strength and long-
strength for the suggested geopolymer concrete. term durability.

Geopolymer concrete has been shown to have better durability


than PCC (Ariffin et al., 2013; Reddy et al., 2012; Sanni and Experimental design
Khadiranaikar, 2012). Bondar et al. (2015) researched the con-
Since compressive strength is the most often used criterion for
sequences of sulfate attack on geopolymer concrete and
opening to traffic, this study focused on the effect of various
reported a loss of compressive strength and percentage of
parameters on the compressive strength of metakaolin geo-
expansion of the alkali-activated natural pozzolan concrete of
polymer mortar. The effect of the silicon dioxide/sodium oxide
up to 19·4% and 0·074, respectively. Vance et al. (2014) studied
(SiO2/Na2O) ratio (using five different ratios) was investigated
the chloride transport resistance of ordinary Portland cement
as a means of accelerating the geopolymerisation process. The
and alkali-activated binder systems. They produced perform-
effect of adding slag or calcium aluminate cement on the
ance-equivalent alkali-activated slag systems that are more sus-
strength of metakaolin geopolymer mortar was also investi-
tainable from energy and environmental standpoints. It has
gated. As a benchmark to check the suggested geopolymer con-
been reported that the production of geopolymeric binders
crete for accelerated pavement repair, Table 1 summarises the
releases 80–90% less carbon dioxide than the production of
minimum required compressive strengths for opening to traffic
Portland cement (Davidovits, 1994). However, to the authors’
currently adopted for conventional PCC in various US states.
knowledge, there is no specific study discussing the freeze–
A geopolymer concrete needs to reach the same level to replace
thaw durability of geopolymer concrete based on metakaolin
conventional PCC for pavement repair purposes.
or fly ash, which is a very important property for a material to
be successfully applied as a repair material.

The aim of this study was therefore to investigate State Compressive strength

Colorado 20·7 MPa (3·0 ksi)


& the factors that affect the mechanical properties and Kansas 24·2 MPa (3·5 ksi)
accelerate the geopolymerisation process of geopolymer Minnesota 20·7 MPa (3·0 ksi)
mortar in order to meet the requirements of early opening Missouri 20·7 MPa (3·0 ksi)
to traffic Nebraska 24·2 MPa (3·5 ksi)
& the effect of these factors on the compressive strength of Oregon 17·3 MPa if a ‘rapid set’ or similar product is
the modified metakaolin geopolymer mortar used
& the freeze–thaw durability of metakaolin geopolymer 20·7 MPa (3·0 ksi) for type I/II/III cement
concrete using the fine-tuned mix ratios. Pennsylvania 20·7 MPa (3·0 ksi) for all repairs except partial
depth
South Dakota Varies depending on time to open to traffic:
Research significance from 24·8 MPa (3·6 ksi) to 27·6 MPa
Portland cement concrete pavements and structures need to be (4·0 ksi)
repaired due to, for example, deterioration, poor ride quality Utah 27·6 MPa (4·0 ksi)
and structural failures. It is widely known that most materials Washington 17·3 MPa (2·5 ksi)
for concrete repair applications today are Portland cement type Wisconsin 20·7 MPa (3·0 ksi)
materials (Fernandez-Jimenez et al., 2006). However, cement
production emits large amounts of atmosphere-polluting Table 1. Minimum required compressive strengths for opening
carbon dioxide (Aleem and Arumairaj, 2012) and consumes for traffic
significant amounts of energy for the required temperature of

47
Downloaded by [ University Of Wollongong] on [08/01/17]. Copyright © ICE Publishing, all rights reserved.
Magazine of Concrete Research Early strength and durability of
Volume 69 Issue 1 metakaolin-based geopolymer concrete
Alanazi, Yang, Zhang and Gao

One way to accelerate the geopolymerisation process is to cure Oxide Mass: %


the geopolymer at elevated temperature, which is complicated
and hard to apply in the field. The most common activating Metakaolin Slag Calcium
solution used to activate alumino-silicate materials is a mixture aluminate
of sodium hydroxide (NaOH) and waterglass (Na2SiO3). A few cement
researchers have investigated the effect of the SiO2/Na2O ratio Aluminium oxide (Al2O3) 40·94 7·34 ≥ 37·0
on the mechanical properties of geopolymer concrete. The Silicon dioxide (SiO2) 55·01 37·95 ≤ 6·0
mechanism of the SiO2/Na2O ratio on accelerating the geo- Potassium oxide (K2O) 0·6 0·36 < 0·2
polymerisation process in geopolymer concrete has been Sodium oxide (Na2O) 0·09 0·27 < 0·2
largely neglected, although it has begun to attract attention Calcium oxide (CaO) 0·14 38·93 ≤ 39·8
recently (Soutsos et al., 2016). The effect of adding aluminate Magnesium oxide (MgO) 0·34 10·22 < 1·5
silicate cement to metakaolin on the geopolymerisation Iron oxide (Fe2O3) 0·55 0·54 ≤ 18·5
process has also been investigated. Aluminate silicate cement Titanium dioxide (TiO2) 0·55 0·39 < 4·0
can harden and set within 1–3 min and is known to have the Chlorides (Cl) 0 0·09 0
quickest hydration reaction of all calcium aluminate minerals Manganese(III) 0 0·55 0
(Rovnanik, 2010). Also, blending slag with other alumino-sili- oxide (Mn2O3)
cate binders has been shown to increase compressive strength Sulfur trioxide (SO3) 0 2·69 < 0·4
and enhance workability (Deb et al., 2014). Thus, to improve Loss on ignition 1·54 1·8 —
the workability of geopolymer mortar, the partial replacement Total 98·22 99·6 —
of metakaolin with slag is also worthy of investigation.
Table 2. Chemical compositions of metakaolin, slag and calcium
In summary, the scope of this study was to evaluate the effect aluminate cement
of different ratios of silicon dioxide/sodium oxide, aluminate
silicate cement and slag on the early strength of geopolymer
mortar for the purpose of finding a rapid curing binder. The
results were compared with the results of a geopolymer mortar The most commonly used alkaline activator to prepare geo-
without the addition of any setting admixtures. polymers is a mixture of sodium hydroxide and sodium silicate
(waterglass). The chemical composition of the sodium silicate
The American Concrete Institute (ACI) defines cold weather as solution used in this study was 9·2% sodium oxide, 28·6%
a period when the mean daily temperature is less than 40°F silicon dioxide and 63·2% water, with a silicon dioxide/sodium
(4·44°C) for more than three continuous days. Attack by cyclic oxide ratio of 3·21. The sodium hydroxide used was in the
freezing and thawing can lead to pavement deterioration due form of flakes of 98% purity. River sand was used to prepare
to cracking and spalling of the concrete surface. The ACI the geopolymer mortar. The alkaline silicate solution was pre-
suggests that the freeze–thaw durability of concrete can be pared 24 h prior to use by dissolving sodium hydroxide flakes
determined by using ASTM C666 (ASTM, 2015) and the in sodium silicate (waterglass).
freeze–thaw durability of concrete is defined as the percent
ratio of the dynamic modulus of elasticity after a number of Specimen preparation
freeze and thaw cycles to the initial value before the freeze– The molar ratio of silicon dioxide/sodium oxide of the water-
thaw cycles (Hamoush et al., 2011). glass solution used in this research was 3·21. The effect of
different molar ratios of silicon dioxide/sodium oxide of the
alkaline solution was studied in order to accelerate the geo-
polymerisation process and gain early high strength. Ratios of
Materials and experimental methods
0·8, 1·0, 1·2, 1·4 and 1·8 of silicon dioxide/sodium oxide of the
Materials alkaline solution were prepared by adding sodium hydroxide
The chemical compositions of the metakaolin, slag and to adjust the molar ratios of silicon dioxide/sodium oxide of
calcium aluminate cement obtained from the suppliers’ data the alkaline solution. The silicon dioxide content comes only
sheets are presented in Table 2. The silica and alumina con- from the sodium silicate solution (waterglass), while sodium
tents in metakaolin account for about 97% of its chemical oxide comes from the waterglass and sodium hydroxide sol-
composition. Slag or blast-furnace slag is a by-product of iron ution. To prepare the geopolymer mortars, metakaolin
making in a blast-furnace. The specific gravity of the slag was and river sand were mechanically mixed for 3 min. Then, the
reported to be 2·89 and, contrary to metakaolin, slag contains alkaline solution was added and mixed for another 5 min with
a high content of calcium oxide. Calcium aluminate cement an additional 65 ml water to enhance the workability of the
possesses good mechanical properties and can gain high early geopolymer mortar. The water/solid ratio was 0·201 for all the
strength when it is used as the primary binder. The specific mixes (the water components being water from the sodium sili-
gravity of the calcium aluminate used was 3·24. cate solution and extra water, and the solid components the

48
Downloaded by [ University Of Wollongong] on [08/01/17]. Copyright © ICE Publishing, all rights reserved.
Magazine of Concrete Research Early strength and durability of
Volume 69 Issue 1 metakaolin-based geopolymer concrete
Alanazi, Yang, Zhang and Gao

metakaolin and sand). The geopolymer mortars comprised


Water/solid

675 g river sand, 225 g metakaolin, 186 g alkaline silicate sol-


0·176
0·179
0·181
0·182
0·185
0·171
0·168
0·179
ratio

ution with five different ratios of silicon dioxide/sodium oxide


and 65 ml water. The geopolymer mortars were moulded into
50 mm cubes and cured at room temperature (20°C) and rela-
tive humidity of 16% for compressive strength testing. These
water: ml

geopolymer mortar specimens were tested at ages of 1, 2 and


Extra

65
65
65
65
65
65
65
65
3 d to investigate the effect of silicon dioxide/sodium oxide
ratio on their early strength, and the best ratio (giving the
highest early strength) was noted.
Silicon dioxide/sodium
oxide molar ratio

The addition of calcium aluminate cement or slag to accelerate


the geopolymerisation process was also investigated. Calcium
aluminate cement was added to the geopolymer mortar at
0·8
1·0
1·2
1·4
1·8
1·0
1·0
1·0

ratios of 20% and 30% by weight of metakaolin; the molar


ratio of silicon dioxide/sodium oxide of these mixes was 1·0. In
another sample, metakaolin in the geopolymer mortar was
replaced with slag (30% by weight), again at a molar ratio of
silicon dioxide/sodium oxide of 1·0; Deb et al., 2014 reported
that the best ratio for replacement of alumino-silicate binder
solution: g
Alkaline

with slag is 30%. All the mix ratios are summarised in Table 3.
252·5

203·5
235
223
216

235
235
235

Compressive strength test


Following ASTM C109/109M (ASTM, 2002), 50 mm cubic
hydroxide : g

specimens were used to measure the compressive strength of


Sodium

the geopolymer mortars. The 1 d compressive strength was


66·5

17·5
49
37
30

49
49
49

measured to provide information regarding the suitability of


the material for use in early opening to traffic pavement
repairs.
Sodium silicate
solution: g

Durability test
186
186
186
186
186
186
186
186

In order to substitute metakaolin-based geopolymer concrete


for ordinary PCC in accelerated pavement repairs, its durability
has to be verified. In the preparation of geopolymer concrete,
metakaolin, fine sand and coarse aggregate were mixed in a
rotating drum mixer with fixed blades for 3 min. The alkaline
Sand:

675
675
675
675
675
675
675
675
g

solution was then added and mixing was continued for


another 5 min with additional water added to enhance the
workability of the geopolymer concrete. The cost of the meta-
Slag:

67·5







g

kaolin-based geopolymer concrete was also reduced since less


alkaline solution and metakaolin were used compared with the
Calcium aluminate

Table 3. Summary of mixture proportions

same volume of geopolymer mortar.


cement: g

67·5

Five geopolymer concrete mixtures, designated mix-1, mix-2,







45

mix-3, mix-4, and mix-5, were prepared. The mix proportions


are listed in Table 4. Immediately after mixing, the fresh geo-
polymer concrete was poured into 75  100  405 mm steel
moulds for rectangular beam specimens and into 75  150 mm
Metakaolin:

disposable plastic moulds to form cylindrical specimens


225
225
225
225
225
225
225
157·5

(Figure 1).
g

All the geopolymer concrete specimens were first cured for


14 d at ambient temperature prior to testing. The specimens
Mix

M1
M2
M3
M4
M5
M6
M7
M8

were then subjected to multiple rapid freeze–thaw cycles in a

49
Downloaded by [ University Of Wollongong] on [08/01/17]. Copyright © ICE Publishing, all rights reserved.
Magazine of Concrete Research Early strength and durability of
Volume 69 Issue 1 metakaolin-based geopolymer concrete
Alanazi, Yang, Zhang and Gao

Ingredient Mix-1 Mix-2 Mix-3 Mix-4 Mix-5

Metakaolin: g 450 360 450 360 360


Slag: g 0 90 0 90 90
Aluminate silicate cement: g 0 0 0 0 90
Fine sand: g 675 675 675 675 675
Coarse aggregate: g 1350 1350 1350 1350 1350
Sodium hydroxide: g 60 60 98 98 60
Sodium silicate solution: g 372 372 372 372 372
Water used to dissolve sodium hydroxide: ml 130 130 130 130 130
Alkaline solution: g 562 562 600 600 562
Water/solid 0·136 0·136 0·134 0·134 0·132
Water/metakaolin 0·810 1·012 0·810 1·012 1·012
Silicon dioxide/sodium oxide molar ratio 1·4 1·4 1·0 1·0 1·4
Curing temperature Room Room Room Room Room

Table 4. Mix proportions of geopolymer concretes

compressive strength of the geopolymer mortars increased with


an increase in curing age.

Five silicon dioxide/sodium oxide molar ratios (0·8, 1·0, 1·2,


1·4 and 1·8) of the alkaline solution were studied and the mix
ratio of the geopolymer mortars was kept constant for all five
different ratios. After 1 d curing, the average compressive
strengths of three samples at ratios of 0·8, 1·0, 1·2, 1·4 and
1·8 were, respectively, 21·23 MPa, 58·01 MPa, 52·97 MPa,
5·55 MPa and 0 MPa, with standard deviations (SD) of
Figure 1. Fresh geopolymer concrete specimens (mix-5) 3·95 MPa, 2·65 MPa, 2·44 MPa, 1·29 MPa and 0 MPa and
coefficients of variation (CoV) of 0·186%, 0·046%, 0·046%,
0·233% and 0%. The maximum compressive strength occurred
for a silicon dioxide/sodium oxide ratio of 1·0 because the
freeze–thaw chamber while the specimens were fully saturated. silica and alumina were highly dissolved at this ratio, which
The dynamic modulus of elasticity, weight loss and compres- accelerates the geopolymerisation process and improves the
sive strength of the geopolymer concrete specimens was compressive strength. However, it was observed that the work-
recorded after 30 freeze–thaw cycles. A Humboldt sonometer ability decreased with a decreased in the silicon dioxide/sodium
was used to find the transverse frequency in order to calculate oxide ratio. In addition, the results show that the compressive
the dynamic modulus of elasticity. In a single cycle, the temp- strength of the metakaolin-based geopolymer mortars
erature in the centre of the concrete sample dropped from increased with curing age.
4·44°C to −17·8°C over 1·5 h; this was followed by a hold at
−17·8°C for 0·5 h, an increase from −17·8°C to 4·44°C for The maximum compressive strength of the geopolymer
1·5 h and a hold at 4·44°C for 0·5 h. One complete cycle thus mortars at a curing age of 1 d was 58·01 MPa, for a silicon
took around 4 h to complete. The relative dynamic modulus of dioxide/sodium oxide molar ratio of 1·0. It can be observed
elasticity (RDME) was calculated every 30 freeze–thaw cycles. from the results that the compressive strength increased when
the molar ratio of silicon dioxide/sodium oxide was increased
from 0·8 to 1·0. On the other hand, the compressive strength
decreased significantly when the silicon dioxide/sodium oxide
Results and discussion
molar ratio was increased from 1·0 to 1·8.
Effect of different silicon dioxide/sodium oxide molar
ratios of the alkaline solution These results indicate an opportunity to control the compres-
The compressive strengths of metakaolin-based geopolymer sive strength and workability of a geopolymer mortar by
mortars with different molar ratios of silicon dioxide/sodium adjusting the molar ratio of silicon dioxide/sodium oxide. The
oxide of the alkaline solution at the ages of 1, 2 and 3 d are decrease in the silicon dioxide/sodium oxide ratio is a result
shown in Table 5 and Figure 2. The results show that the of increasing sodium hydroxide in the alkaline solution.

50
Downloaded by [ University Of Wollongong] on [08/01/17]. Copyright © ICE Publishing, all rights reserved.
Magazine of Concrete Research Early strength and durability of
Volume 69 Issue 1 metakaolin-based geopolymer concrete
Alanazi, Yang, Zhang and Gao

Curing age: d Silicon dioxide/sodium oxide Compressive strength: MPa (ksi) SD: MPa (ksi) CoV: %

1 0·8 21·23 (3·1) 3·95 (0·57) 0·19


1·0 58·01 (8·41) 2·65 (0·38) 0·05
1·2 52·97 (7·68) 2·44 (0·35) 0·05
1·4 5·55 (0·80) 1·29 (0·19) 0·23
1·8 0 (0) 0·00 (0) 0·00
2 0·8 47·07 (6·83) 0·94 (0·14) 0·02
1·0 66·83 (9·69) 2·60 (0·38) 0·04
1·2 64·07 (9·29) 1·67 (0·24) 0·03
1·4 59·23 (8·59) 0·98 (0·14) 0·02
1·8 0 (0) 0·00 (0) 0·00
3 0·8 49·6 (7·19) 2·05 (0·30) 0·04
1·0 67·5 (9·79) 3·33 (0·48) 0·05
1·2 64·74 (9·39) 0·65 (0·09) 0·01
1·4 59·67 (8·65) 1·39 (0·20) 0·02
1·8 5·38 (0·78) 0·60 (0·09) 0·11

Table 5. Compressive strength of geopolymer mortars at five


different ratios of silicon dioxide/sodium oxide

80
0·8 1·0 1·2 1·4 1·8
67·5 Curing Mix Compressive SD: MPa CoV: %
Compressive strength: MPa

70 66·83
64·07 64·74
58·01 59·23 59·67 time: h strength: MPa (ksi) (ksi)
60 52·97
49·6
50 47·07 8 M6 8·78 (1·27) 0·63 (0·09) 0·07
40 M7 7·90 (1·15) 0·28 (0·04) 0·04
24 M6 43·38 (6·29) 0·43 (0·06) 0·01
30
21·23 M7 39·13 (5·68) 0·96 (0·14) 0·03
20
72 M6 48·33 (7·01) 1·54 (0·22) 0·03
10 5·55 5·38
M7 55·97 (8·12) 1·73 (0·25) 0·03
0 0
0
1 2 3
Table 6. Effect of calcium aluminate cement on compressive
Curing time: d strength of geopolymer mortar

Figure 2. Average compressive strength of geopolymer mortar


with different ratios of silicon dioxide/sodium oxide (0·8, 1·0, 1·2,
1·4 and 1·8) at curing ages of 1, 2 and 3 d ratio of 1·0 produced the highest compressive strength, and
this ratio was thus selected for further study with the addition
of other accelerated setting materials in order to shorten the
time for opening to traffic.
According to Škvára et al. (2006), sodium plays an important
role in the formation of a geopolymer, since it acts as charge
balancing ions. However, adding more sodium silicate would Effect of adding calcium aluminate cement to
result in a decrease in compressive strength, because excess metakaolin
sodium silicate prevents water from evaporating and hinders Reaching high early strength within 8 h increases the opportu-
structural formation. nity of geopolymers to be used in concrete pavement repairs
with priority for early opening to traffic. In this study, calcium
The investigation of the use of different molar ratios of silicon aluminate cement (ratios of 20% and 30% to metakaolin by
dioxide/sodium oxide in the alkaline solution indicates an weight) was added to geopolymer mortar to shorten the
acceleration of the geopolymerisation process and early strength setting time. The effect of adding calcium aluminate cement
gains of the geopolymer mortar. Silicon dioxide/sodium oxide on compressive strength is shown in Table 6 and Figure 3. The
ratios of 0·8, 1·0 and 1·2 were found to produce the strength results show that the addition of calcium aluminate cement
required by various departments of transport to open to traffic reduced the setting time and decreased the compressive
within 24 h (Table 1). A silicon dioxide/sodium oxide molar strength at 24 h (compared with the compressive strength of

51
Downloaded by [ University Of Wollongong] on [08/01/17]. Copyright © ICE Publishing, all rights reserved.
Magazine of Concrete Research Early strength and durability of
Volume 69 Issue 1 metakaolin-based geopolymer concrete
Alanazi, Yang, Zhang and Gao

60 55·97 Freeze–thaw durability of metakaolin-based


M6 M7 geopolymer concrete with added slag
Compressive strength: MPa

48·33
50
43·38 The weight loss results of all five geopolymer concrete mix
39·13
40 ratios after 30 freeze–thaw cycles in accordance with ASTM
C666 are listed in Table 8, together with the RDME values.
30
The mix-1 specimens experienced the highest weight loss,
20 which was four times higher than that of the mix-3 specimens.
8·78 7·9 Both the mix-2 and mix-4 specimens experienced less weight
10
loss than the other specimens with the same molar ratio of the
0 alkaline solution but without the addition of slag. From the
8 24 72 results, it can be concluded that a geopolymer concrete with
Curing time: h higher water content is less frost resistant than one with lower
water content. In addition, freeze–thaw cycles have a signifi-
Figure 3. Average compressive strength of geopolymer mortar cant effect on the durability of the geopolymer concrete.
with different levels of added calcium aluminate cement (20%, According to the ASTM C666 standard test (procedure A),
M6; 30% M7) at curing ages of 8, 24 and 72 h mix-3 and mix-4 give the best durability compared with the
other mixtures, since they lost less than 5% of their weight.
The weight loss observed was mainly due to spalling of the
mortar with a silicon dioxide/sodium oxide ratio of 1·0 concrete surface as a result of freeze–thaw action. However, the
without any accelerator). In addition, waterglass works as a results indicate a significant loss of weight and RDME after
retarder on the hydration of calcium aluminate cement. There only 30 cycles. Compared with conventional concrete with 5%
were no significant differences in compressive strength when air entraining agent, it seems the metakaolin geopolymer con-
calcium aluminate cement was added in the ratios of 20% and crete in its current mix is less durable than conventional con-
30% of metakaolin weight, but workability was low at the 30% crete. However, a metakaolin geopolymer concrete mix with
replacement level. air entrainment might change this conclusion, and this will be
researched in the next phase of this project.

Effect of partially replacing metakaolin with slag Conclusions


Blending slag with metakaolin was investigated to reduce Experimental work was carried out to investigate the effect of
setting times and adjust paste workability. Metakaolin was the molar ratio of silicon dioxide/sodium oxide of the alkaline
partially replaced with slag at a ratio of 30% by weight for a solution, the addition of calcium aluminate cement to meta-
silicon dioxide/sodium oxide ratio of 1·0. Table 7 summarises kaolin and the partial replacement of metakaolin with slag on
the effect of slag replacement on the compressive strength of the early compressive strength of geopolymer mortars. The
the geopolymer mortar. major conclusions from this study are as follows.

Although slag has been reported to enhance the compressive (a) All the factors studied were found to have a tremendous
strength and reduce the setting time in fly ash geopolymer influence on the early compressive strength of the
mortar due to the calcium content in slag, the results obtained geopolymer mortars.
in this study show that slag negatively affects the compressive (b) A silicon dioxide/sodium oxide molar ratio of 1·0 was
strength and increases the setting time in metakaolin geopoly- found to be the optimum ratio for accelerating the
mer mortar, partially due to the different difficulty levels of geopolymerisation process and enhancing the compressive
forming C-A-S-H in these two mixes. However, slag increased strength.
the workability of the geopolymer mortar. (c) Calcium aluminate cement can be used as an accelerator
for the geopolymer; the best addition ratio of calcium
aluminate cement to metakaolin was found to be 20% by
Curing Compressive strength: SD: MPa CoV: %
time: h MPa (ksi) (ksi)
Mix-1 Mix-2 Mix-3 Mix-4 Mix-5
8 0·00 (0) 0·00 (0) 0·00
24 13·48 (1·96) 0·90 (0·13) 0·07 Weight loss: % 6·86 5·82 1·88 1·29 6·31
72 44·57 (6·46) 0·97 (0·14) 0·02 RDME: % — — 46·21 37·72 37·88

Table 7. Effect of slag replacement on the compressive strength Table 8. Weight loss and relative dynamic modulus of elasticity
of geopolymer mortar (mix M8) (RDME) after 30 freeze–thaw cycles

52
Downloaded by [ University Of Wollongong] on [08/01/17]. Copyright © ICE Publishing, all rights reserved.
Magazine of Concrete Research Early strength and durability of
Volume 69 Issue 1 metakaolin-based geopolymer concrete
Alanazi, Yang, Zhang and Gao

weight. Calcium aluminate cement plays a significant Deb PS, Nath P and Sarker PK (2014) The effects of
role in accelerating the geopolymerisation process and ground granulated blast-furnace slag blending with fly ash
results in faster strength gain and higher compressive and activator content on the workability and strength
strength. properties of geopolymer concrete cured at ambient
(d) A mix of slag blended with metakaolin was found to have temperature. Materials & Design 62(10): 32–39.
less compressive strength than metakaolin alone. Duxson P, Provis JL, Lukey GC and Van Deventer JS (2007) The
(e) Geopolymers could be a good candidate for pavement role of inorganic polymer technology in the development
repairs, especially those specified for opening early to of ‘green concrete’. Cement and Concrete Research 37(12):
traffic. However, durability needs to be carefully studied. 1590–1597.
The current research results show that mix ratios and Fernandez-Jimenez AM, Palomo A and Lopez-Hombrados C
additives have an important effect on the durability of (2006) Engineering properties of alkali-activated fly ash
metakaolin geopolymer concrete. concrete. ACI Materials Journal 103(2): 106–112.
Fu CC and Larmie EA (2005) Rehabilitation and Maintenance of
Road Pavements using High Early Strength Concrete.
Maryland State Highway Administration, Baltimore, MD,
REFERENCES USA, Report MD-05-SP208B49.
Alanazi H, Yang M, Zhang D and Gao Z (2016) Bond strength of Gourley JT (2003) Geopolymers: opportunities for
PCC pavement repairs using metakaolin-based geopolymer environmentally friendly construction materials. In Materials
mortar. Journal of Cement and Concrete Composites 65(1): 2013: Conference on Adaptive Materials for a Modern Society
75–82. (Williams J (ed.)). Institute of Materials Engineering
Aleem MA and Arumairaj PD (2012) Geopolymer concrete – a Australasia, Melbourne, Australia, pp. 211–216.
review. International Journal of Engineering Sciences and Hamoush S, Picornell-Darder M, Abu-Lebdeh T and Mohamed A
Emerging Technologies 1(2): 118–122. (2011) Freezing and thawing durability of very high
Ariffin MAM, Bhutta MAR, Hussin MW, Mohd Tahir M and strength concrete. American Journal of Engineering and
Aziah N (2013) Sulfuric acid resistance of blended ash Applied Sciences 4(1): 42–51.
geopolymer concrete. Construction and Building Materials Hardjito D, Wallah SE, Sumajouw DMJ and Rangan BV (2004)
43(6): 80–86. The stress–strain behavior of fly ash-based geopolymer
ASTM (2002) C109: Standard test method for compressive concrete. In Development in Mechanics of Structures &
strength of hydraulic cement mortars (using 2-in. or Materials (Decks AJ and Hao H (eds)). Balkema, Leiden,
[50-mm] cube specimens). ASTM International, West the Netherlands, pp. 831–834.
Conshohocken, PA, USA. Hardjito D, Wallah SE, Sumajouw DMJ and Rangan BV (2005)
ASTM (2015) C666/C666M-15: Standard test method for Introducing fly ash -based geopolymer concrete:
resistance of concrete to rapid freezing and thawing. manufacture and engineering properties. Proceedings of
ASTM International, West Conshohocken, PA, USA. 30th Conference on Our World in Concrete and Structures
Bondar D, Lynsdale CJ, Milestone NB and Hassani N (2015) International Conference (Tam CT, Ong KCG and Tan TH
Sulfate resistance of alkali activated pozzolans. (eds)). Singapore, paper 100030032.
International Journal of Concrete Structures and Materials Kamarudin H, Al Bakri AM, Binhussain M et al. (2011)
9(2): 145–158. Preliminary study on effect of NaOH concentration on
Buch N, Van Dam TJ, Peterson K and Sutter L (2008) Evaluation early age compressive strength of kaolin-based green
of high-early strength PCC mixtures used in full depth cement. In Proceedings of International Conference on
repairs. Construction and Building Materials 22(3): Chemistry and Chemical Process IPCBEE (Dan Y (ed.)).
162–174. Bangkok, Thailand, vol. 10, pp. 18–24.
Davidovits J (1988) Structural characterization of geopolymeric Montes C and Allouche EN (2012) Evaluation of the potential
materials with x-ray diffractometry and mas NMR of geopolymer mortar in the rehabilitation of buried
spectroscopy. Proceedings of Geopolymer ’88 – First infrastructure. Structure and Infrastructure Engineering
European Conference on Soft Mineralurgy (Davidovits J 8(1): 89–98.
and Orlinaski J (eds)). Saint Quentin, France, pp. 149–166. Reddy DV, Edouard JB and Sobhan K (2012) Durability of fly
Davidovits J (1994) Properties of geopolymer cements. In ash–based geopolymer structural concrete in the marine
Proceedings of 1st International Conference on Alkaline environment. Journal of Materials in Civil Engineering
Cements and Concretes (Davidovits J (ed.)). Kiev State 25(6): 781–787.
Technical University, Kiev, Ukraine, vol. 1, pp. 131–149. Rovnanik P (2010) Influence of C12 A7 admixture on setting
Davidovits J (1999) Chemistry of geopolymeric system properties of fly ash geopolymer. Ceramics-Silikáty 54(4):
terminology. Proceedings of the 2nd International 362–367.
Conference on Geopolymer ’99 (Davidovits J (ed.)). Sanni SH and Khadiranaikar RB (2012) Performance of
Saint Quentin, France, pp. 9–39. geopolymer concrete under severe environmental

53
Downloaded by [ University Of Wollongong] on [08/01/17]. Copyright © ICE Publishing, all rights reserved.
Magazine of Concrete Research Early strength and durability of
Volume 69 Issue 1 metakaolin-based geopolymer concrete
Alanazi, Yang, Zhang and Gao

conditions. International Journal of Civil & Structural based on OPC and alkali-activated slag binders.
Engineering 3(2): 396–407. International Journal of Concrete Structures and Materials
Škvára F, Kopecký L, Nemecek J and Bittnar Z (2006) 8(4): 289–299.
Microstructure of geopolymer materials based on fly ash. Xu H and van Deventer JSJ (2000) The geopolymerisation of
Ceramics-Silikaty 50(4): 208–215. alumino-silicate minerals. International Journal of Mineral
Soutsos M, Boyle AP, Vinai R, Hadjierakleous A and Barnett SJ Processing 59(3): 247–266.
(2016) Factors influencing the compressive strength of fly Yang M, Abdelrahman M, Ahmari S and Alanazi H (2013) Survey
ash based geopolymers. Construction and Building and Literature Review of Fast-Track PCC Pavement Repair
Materials 110(5): 355–368. Processes and Materials. NDSU-2013-02 SPRR-034(010).
Van Dam TJ (2005) Guidelines for Early-Opening-to-Traffic North Dakota Department of Transportation, Bismarck,
Portland Cement Concrete for Pavement Rehabilitation ND, USA.
(No. 540). Transportation Research Board, Washington, Zhang Z, Yao X and Zhu H (2010) Potential application
DC, USA. of geopolymers as protection coatings for marine
Vance K, Aguayo M, Dakhane A et al. (2014) Microstructural, concrete: I. Basic properties. Applied Clay Science
mechanical, and durability related similarities in concretes 49(1): 1–6.

HOW CAN YOU CONTRIBUTE?


To discuss this paper, please submit up to 500 words to
the editor at journals@ice.org.uk. Your contribution will
be forwarded to the author(s) for a reply and, if con-
sidered appropriate by the editorial board, it will be pub-
lished as a discussion in a future issue of the journal.

54
Downloaded by [ University Of Wollongong] on [08/01/17]. Copyright © ICE Publishing, all rights reserved.