Construction and Building Materials 98 (2015) 685–691

Contents lists available at ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Mechanical properties of alkali activated flyash/Kaolin based

geopolymer concrete
F.N. Okoye a, J. Durgaprasad a, N.B. Singh b,⇑
a
Department of Civil Engineering, Sharda University, Greater Noida, India
b
Research and Technology Development Centre, Sharda University, Greater Noida, India

h i g h l i g h t s

 Geopolymer concretes reduce green house gas emissions.

 Geopolymer concretes were made by fly ash, kaolin, alkalies and sodium silicate.
 NaOH gave higher compressive strength as compared to KOH.
 Combination of 50% FA and 50% Kaolin gave maximum strength.

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

Article history: Five geopolymer concrete mixes were casted using Fly ash, Kaolin, sodium hydroxide, potassium
Received 5 March 2015 hydroxide, sodium silicate and aggregates. Portland cement concrete (M30) was used as a reference sam-
Received in revised form 18 July 2015 ple. The effect of temperature, sodium and potassium hydroxides and different superplasticizers on the
Accepted 4 August 2015
compressive strength was studied. Portland cement concrete with the same mixture proportion was also
Available online 2 September 2015
casted as control. A total of 245 cubes of 100 mm  100 mm were crushed including the trial experi-
ments. The cubes were cured in oven at different temperatures (40 °C, 60 °C, 80 °C, 100 °C and 120 °C).
Keywords:
The results have shown that the compressive strengths increased with increasing temperature, curing
Geopolymer
Cement
time and type of alkali activators. Naphthalene sulfonate based superplasticizer performed better than
Concrete other superplasticizers. The compressive strength in the presence of 1.0% Naphthalene sulfonate
Kaolin superplasticizer was found 23.3% and 30.9% higher than in the presence of Melamine–formaldehyde
Fly ash and Polycarboxylate ester respectively. Mechanism of strength development has been discussed.
Compressive strength Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction environmentally friendly concrete, which can lower CO2 emission,

is the development of inorganic alumino-silicate polymer, called
Portland cement is one of the most important components of geopolymer, synthesized from materials of geological origin or
concrete. With the increase of population, the demand for Ordinary by-product materials such as Fly ash that is rich in silicon and alu-
Portland cements (OPC) increases. In general 1 tone of cement minum [6–8]. There is a growing volume of scientific literature
production generates 1 tone CO2 gas. The cement industry is exploring the properties of geopolymeric materials on the labora-
second only to power generation in the production of CO2 and tory scale and number of research papers on geopolymer cements
accounts for 7–8% of the planet’s human-produced CO2 emissions using Fly ash has been published [9–14]. However, in the present
[1–3]. Attempts are being made to reduce CO2 emissions and lower paper Fly ash is replaced with different amounts of Kaolin and
the energy consumption. One of the alternatives to produce more the mechanical properties of geopolymer concretes have been
environmentally friendly concrete is to replace the amount of studied in detail.
OPC in concrete with by-product materials such as Fly ash in the
form of blended cement [4,5]. However, the major drawbacks of 2. Experimental
blended cements are low early strength. Another way to have
2.1. Materials

⇑ Corresponding author. Low calcium Fly ash conforming to the requirements of ASTM C618 (Class F)
E-mail addresses: okoyefrancis2012@gmail.com (F.N. Okoye), nbsingh43@gmail. and Kaolin were used in this investigation. Commercially available Kaolin and the
com (N.B. Singh). Fly ash obtained from National Power Station, Dadri, Uttar Pradesh, India, were

http://dx.doi.org/10.1016/j.conbuildmat.2015.08.009
0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
686 F.N. Okoye et al. / Construction and Building Materials 98 (2015) 685–691

used during the experiments. OPC was used for making OPC concrete for comparing Table 3
the compressive strengths of geopolymer concretes. The chemical compositions of Physical properties of gravels and sand.
OPC, Fly ash and Kaolin are given in Table 1. Coarse aggregates of sizes 20 mm and
10 mm and river sand as fine aggregate were used. Sieve analyses were performed Sample Sp. Gravity Water absorption (%) Fineness modulus
to determine the particle size distribution as per BS 812, Part1, 1975 and given in 20 mm aggregate 2.5 0.17 2.7
Table 2. Physical properties of gravels and sand are given in Table 3. Distilled water 10 mm aggregate 2.4 0.87 2.8
was used in all the experiments. Naphthalene sulfonate (N.S), Malamine–formalde- Sand 2.6 – 2.1
hyde (GN-51) and Polycarboxylate ester (Chryso-730) based superplasticizers were
used as admixtures. The alkali activators used were solutions of sodium hydroxide,
potassium hydroxide and sodium silicate. 2.4. Casting of geopolymer concrete mixes

The conventional techniques used in OPC concrete were adopted. First fine and
2.2. Preparation of alkalies coarse aggregates were saturated surface dry (SSD) and then mixed together in
600 mm  900 mm mixing pan for about 3 min. The alkali solution was mixed with
Solutions of sodium and potassium hydroxides (14 M each) were prepared superplasticizer and then added to the dry materials and mixing continued for
separately. The solutions prepared were left for 24 h before mixing with sodium 2 min. The whole mixture was then transferred into a tilting type drum concrete
silicate. The mixtures of sodium hydroxide/potassium hydroxide and sodium mixer and mixing continued for 3–5 min. The fresh geopolymer concrete formed
silicate solutions were left for 1 day and then used for geopolymerization process. pellets when homogeneously mixed in a drum concrete mixer and were very stiff
in consistency as far as workability was concerned; however, adequate compaction
2.3. Mix proportion of geopolymer concrete was achieved. The mixture was casted in a 100 mm  100 mm steel mold in three
layers, and each layer given 60 strokes with 20 mm compacting rod. Eight cubes
The geopolymer concrete was prepared by conventional method as OPC were casted for each mix beside the trial mixes. The casted samples were left in
concrete. Since the density of geopolymer concrete is almost equal to that of OPC the laboratory at room temperature for 48 h (Fig. 1).
concrete (2400 kg/m3), aggregates also occupy 75–80% by mass in geopolymer con-
cretes [15]. In the present mix design of geopolymer concrete, coarse and fine 2.5. Curing of geopolymer concrete
aggregates were taken as 77% by mass of the entire mixture. Fine aggregates were
30% by mass of the total aggregates. The ratio of sodium silicate to sodium hydrox- The process of polymerization requires high temperature and in order to know
ide solution was kept 2.5. 14 M NaOH solution was used. To improve the workabil- the optimum curing temperature Mix4 after demolding was heated at different
ity of fresh geopolymer mix, Naphthalene sulfonate based superplasticizer was temperatures for 72 h. After demolding, all the samples (Mix1, Mix2, Mix3, Mix4
used in all the mixes. In order to compare the effectiveness of different superplas- and Mix5) were transferred in the oven for heat curing at 100 °C for 72 h. The
ticizers on compressive strength of geopolymer concrete, different doses of super- samples were then left at room temperature after curing until the day of testing.
plasticizers (Naphthalene sulfonate, Malamine–formaldehyde and Polycarboxylate
ester based superplasticizers) were added separately to Mix4 and compressive 2.6. Effect of KOH on compressive strength
strengths were measured. Six mixes were made. Amounts of fine and coarse aggre-
gates, superplasticizers and alkali were kept constant while Fly ash was partly Mix5 given in Table 4 was prepared by using 14 M KOH in place of 14 M NaOH
replaced by Kaolin as given in Table 4. Four mixes Mix1, Mix2, Mix3 and Mix4 of and the compressive strengths were determined at different intervals of time as in
geopolymer concretes using NaOH were prepared and their compositions are given the presence of NaOH.
in Table 4. Fifth Mix designated as Mix5 was also prepared by using KOH (14 M)
instead of NaOH. A control mix with Portland cement (M30) was prepared in order
2.7. Fourier transform infrared (FTIR) spectral studies
to compare with those of geopolymer concretes. The detailed mix design of
geopolymer concrete mixes is given in Table 4.
FTIR spectra were recorded in KBr phase in the frequency range 400–
4000 cm 1.

Table 1
2.8. TG/DTG/DTA studies
Chemical composition of OPC, Fly ash and Kaolin.

Constituents Composition (%) TG/DTG/DTA of geopolymer cements were recorded from room temperature to
800 °C in N2 atmosphere at a heating rate of 10 °C/min.
OPC Fly ash Kaolin
Loss on ignition 2.48 3.79 13.97 2.9. SEM studies
Silicon oxide (SiO2) 19.01 50.7 45.3
Calcium oxide (CaO) 66.89 2.38 0.05 SEM pictures of Mix1 were recorded with Quanta FEG 250 ESEM instrument.
Magnesium oxide (MgO) 0.81 1.39 0.25
Phosphate (P2O5) 0.08 – –
Sodium oxide (Na2O) 0.09 0.84 0.27 3. Results and discussion
Potassium oxide (K2O) 1.17 2.40 0.44
Manganese oxide (MnO) 0.19 – – 3.1. FTIR studies
Aluminum oxide (Al2O3) 4.68 28.80 38.38
Iron oxide (Fe2O3) 3.20 8.80 0.30
In order to confirm the formation of geopolymer, FTIR spectra
were recorded (Fig. 2). A strong peak at 1000 cm 1 in all the three
samples is associated with Al–O and Si–O asymmetric stretching
Table 2
Sieve analysis of aggregates. vibrations, characteristic of geopolymerization [16] and the pres-
ence of a zeolitic precursor (amorphous aluminosilicate network
BS sieve size (mm) Percentage passing of aggregates of different size
structure) [17]. A broad band in the region 3400–3600 may be
20 mm 10 mm Fine aggregates due to stretching vibrations of OH groups from the water mole-
(aggregate) (aggregate) (aggregate)
cules. The amorphous nature of the geopolymer is affected by
25 100 100 – the type of alkali cation [17,18]. It is well known that variation in
20 95.6 94.8 –
the ratio SiO2/Na2O significantly modifies the degree of polymer-
12.5 26.4 19.1 –
10 6.2 4.4 –
ization of the dissolved species in an alkaline silicate solution
4.75 0.5 0 100 [18,19]. This plays a significant role in determining the structure
2.36 – – 98.95 and properties of geopolymer gels.
1.18 – – 84.65
0.60 – – 59.5
0.30 – – 34.1
3.2. Thermal studies
0.15 – – 2.5
Pan In order to know the thermal stability of geopolymers, TG/DTG/
DTA studies were made (Fig. 3). The weight loss starts at around
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Table 4
Mix proportion of geopolymer concrete.

MIX No. Quantity of ingredients (kg/m3)

Coarse aggregate Fine sand Fly ash Kaolin OPC SS NaOH (14 M) KOH (14 M) SP ALK/binder W/S
20 mm 10 mm
Mix1 862 431 554 388 0 0 113 45 – 4.0 0.4 0.2
Mix2 862 431 554 0 388 0 113 45 – 4.0 0.4 0.2
Mix3 862 431 554 349.2 38.8 0 113 45 – 4.0 0.4 0.2
Mix4 862 431 554 194 194 0 113 45 – 4.0 0.4 0.2
Mix5 862 431 554 194 194 0 113 45 4.0 0.4 0.2
M30 862 431 554 0 0 388 N.A N.A – 4.0 N.A 0.2

FA – Fly ash, SS – sodium silicate, SP – superplasticizers, ALK – alkaline, W/S – water/solid ratio.

Fig. 1. Samples after casting.

100 °C in all the cases as indicated by the curves, so optimum tem-

perature of curing is about 100 °C. However at higher temperatures
the curves become complex and differ from each other. This may
be due to varying extent of polymerizations. The structural transi-
tion from amorphous to crystalline of geopolymers synthesized at
low to mild temperatures in concentrated slurries also implies that
the synthesis temperature and aging are critical in determining the
structure of the reaction products [20].

3.3. Effect of temperature on compressive strength

The effect of temperature on compressive strength of Mix4 at

7 days is shown in Fig. 4. The results show that the compressive
strength increased with temperature up to 100 °C and decreased
at 120 °C. Other researchers [20] reported higher compressive Fig. 2. FTIR spectra of: 1. 50% FA + 50% Kaolin–sodium silicate–sodium hydroxide
strength with increased temperature up to 90 °C. Curing of geopolymer cured at 100 °C, 2. 100% FA–sodium silicate–sodium hydroxide
geopolymer cured at 100 °C and 3. 1. 50% FA + 50% Kaolin–sodium silicate–KOH
geopolymer concrete up to 90 °C does not decrease the compres- geopolymer cured at 100 °C.
sive strength as reported [21]. It is possible that higher tempera-
ture causes excessive loss of moisture and subsequent cracks in
the specimen, which produce void thereby resulting in the loss of
strength [22]. Com:Str:OPC concr : > Com:Str:Fly ash based Geopolymer concr :
> Com:Str:Kaolin based Geopolymer concr :
3.4. Compressive strengths of Fly ash and Kaolin based-geopolymer
concrete The lower values of compressive strengths of geopolymer con-
cretes may be attributed due to the presence of voids that was
Variations of compressive strength of Fly ash and Kaolin based- noticed after heat curing. This might have resulted due to poor sur-
geopolymer concretes and that of OPC based concrete are shown in face texture of the geopolymer concretes. Air voids in general dis-
Fig. 5. It is observed that OPC has the maximum value of compres- rupts the packing of binder (Fly ash and Kaolin) and increase the
sive strength at all the times. The variations of compressive heterogeneity in the microstructure SEM picture (Fig. 6) shows
strength followed the sequence. poor surface texture and heterogeneous structure. As a result the
688 F.N. Okoye et al. / Construction and Building Materials 98 (2015) 685–691

Fig. 3. TG/DTG/DTA curves.

 F.N. Okoye et al. / Construction and Building Materials 98 (2015) 685–691 689

Fig. 4. Effect of temperatures on the compressive strength of Mix4.

Fig. 7. Effect of partial replacement of Fly ash with Kaolin on compressive strength
of geopolymer concrete. (Remove OPC concrete from the figure.)

3.5. Effect of partial replacement of Fly ash with Kaolin on compressive

strength of geopolymer concrete

The effect of partial replacement of Fly ash with Kaolin in

geopolymer concrete on compressive strength was investigated
and the results are given in Fig. 7. The samples were cured at
100 °C and the compressive strengths were measured up to
28 days. The results show that in the concrete where 50% Fly ash
was replaced with 50% Kaolin, the compressive strength was much
higher than when only 10% FA was replaced by Kaolin. The differ-
ences in compressive strengths may be due to differences in the
composition, structure, particle size and dissolution rates of Kaolin
and Fly ash [20]. The base structure of Kaolin is that of a highly
disrupted phyllosilicate structure containing mostly silicon and
aluminum and there is very little heterogeneity in the size of
particles. In contrast, Fly ash is an industrial waste and made up
Fig. 5. Compressive strengths of Kaolin and Fly ash based geopolymer concretes
of silicon, aluminum and iron oxides, as well as significant
and OPC concrete.
amounts of calcium. The particles in Fly ash are generally spherical,
but inhomogeneous, and comprise glassy as well as crystalline
(often mullite and quartz) phases. The particle size distribution
can be very broad, and different size fractions will differ in elemen-
tal and phase composition. These differences affect the polymer-
ization process and the compressive strength to a large extent.

3.6. Effect of different grades of super plasticisers on compressive

strength of geopolymer concrete

The effect of different superplasticizers on the compressive

strength of Mix4 at seven days of curing time was studied and
the results are shown in Fig. 8 and given in Table 5. It is found that
1.0 wt% Naphthalene based superplasticizer gave maximum
strength. Higher doses decreased the strength. Effectiveness of
superplasticizers on compressive strength is as follows.

Naphthalene based SP > Melamine formaldehyde based SP

> Polycarboxylate ester based SP:

3.7. Effect of potassium hydroxide on compressive strength

Fig. 6. SEM picture of Mix1 concrete.
Mix5 was prepared by using 14 M potassium hydroxide. Five
cubes were casted in 100 mm  100 mm steel molds. The cubes
compressive strength is decreased. However, the strengths of Kao- were cured in an oven at 100 °C for 72 h and left at room temper-
lin and Fly ash based Geopolymer concretes are sufficient enough ature until the day of testing. The result was compared with Mix4
for casting. (Fig. 9). Fig. 9 showed that sodium hydroxide performed better
690 F.N. Okoye et al. / Construction and Building Materials 98 (2015) 685–691

when higher silicate activating solutions are used. It is also

reported that the sodium cations have better zeolitization capabil-
ities in geopolymer forming systems [26], possibly because they
are smaller than potassium cations and therefore able to migrate
easily through the moist gel network.

4. Conclusions

Results showed that materials of geological origin which are

rich in aluminum silicate are good materials for geopolymer con-
crete especially when blended with Fly ash. Replacement of Fly
ash with 50% Kaolin showed positive effect on the geopolymeriza-
tion process and the compressive strength was found much higher
as compared to the concrete made from OPC. On the other hand
when FA was replaced by 10% Kaolin, the compressive strength
was found to be lower as compared to that of concrete made from
OPC. The strength development of Fly ash and Kaolin based
geopolymer concrete compared favorably with OPC concrete. The
Fig. 8. Effect of different superplasticizers on compressive strength of geopolymer
compressive strength of geopolymer concrete increased with age.
concrete.
Addition of super plasticisers increased the workability of geopoly-
mer concrete and Naphthalene based superplasticizer performed
Table 5 better than other superplasticizers. The preparation of geopolymer
Compressive strength of Mix4 with different grades of superplasticizers (N/mm2). concrete did not require OPC, hence the problem of green house
Percentage Naphthalene Melamine– Polycarboxylate emission could be reduced drastically.
dosage sulfonate (N.S) formaldehyde ester
(GN-51) (Chryso-730)
Acknowledgements
1.0 46.6 37.8 35.6
1.5 46.0 29.5 25.3
2.0 44.7 35.1 31.6 One of us (FNO) expresses profound gratitude to Federal gov-
2.5 39.4 31.6 30.7 ernment of Nigeria for financial support through TET FUND, with-
3.0 36.0 28.6 28.3 out which, it wouldn’t have been possible to carry out this research
work. We are also thankful to Federal Polytechnic Oko, Nigeria for
moral support. The authors are also thankful to Prof. B. Middendorf
of University of for providing facilities for recording SEM pictures.

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