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A mix design procedure for geopolymer concrete with fly ash

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DOI: 10.1016/j.jclepro.2016.05.041

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 Journal of Cleaner Production 133 (2016) 117e125

Contents lists available at ScienceDirect

Journal of Cleaner Production

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

A mix design procedure for geopolymer concrete with fly ash

P. Pavithra a, M. Srinivasula Reddy a, Pasla Dinakar a, *, B. Hanumantha Rao a,
B.K. Satpathy b, A.N. Mohanty b
a
School of Infrastructure, Indian Institute of Technology, Bhubaneswar, Odisha 751013, India
b
National Aluminium Company Limited (NALCO), Bhubaneswar 751013, India

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

Article history: Effective promotion of GPC is required in order to minimize the environment threat due to fly ash waste
Received 20 October 2015 disposal and reduce cement consumption. To achieve this, specific mix design procedure for develop-
Received in revised form ment of GPC is essential. Therefore, efforts have been made in this paper to develop a mix design
7 May 2016
methodology for GPC with the main focus on achieving better compressive strength in an economical
Accepted 7 May 2016
Available online 24 May 2016
way for different alkaline solutions to binder proportions. Low calcium fly ash brought from local sources
as the binder material, sodium hydroxide and sodium silicate as alkaline activator solutions, and
aggregate grading based on DIN standards, have been employed for conducting experimental investi-
Keywords:
Activator solution
gation. Correlation between the alkaline activator solution to binder ratios and 28 day compressive
Compressive strength strength has been investigated to propose conceptual mix design method for GPC in a rational way. Mix
Fly ash design is proposed for various AAS/FA ratios ranging from 0.4 to 0.8, and the 28 day compressive strength
Geopolymer concrete as high as 54 MPa has been noticed. The design methodology proposed has been given step-wise and the
Mix design same has been verified with the help of an example in this paper.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction investigation into alternative to cement products with reduced

Nowadays, the increase in the people's attention on the con-
servation of natural resources and minimization of environment
depletion has led to look at the alternatives to accustomed con-
struction materials. Currently, ordinary Portland cement based
concrete is the leading construction material all across the world,
with the cement usage being 4.0 billion tons per annum and growth
rate being 4% per annum (Mineral Commodities Summary, 2014).
The major problems associated with the Portland cement are its
production, which is energy consuming and more significantly it
releases very high volume of carbon dioxide in to the atmosphere.
At the same time the disposal of industrial wastes such as fly ash,
ground granulated blast furnace slag, mine waste, red mud etc, has
become a big problem, it requires large areas of useful land and also
has huge impact on the environment. Therefore, the need is
emanated from further investigation into safe waste disposal and
Abbreviations used: AAS, Alkaline Activator Solution; AAS/FA, Alkaline Activator
Solution to Fly Ash; GPC, GeoPolymer Concrete; NaOH, Sodium hydroxide; Na2SiO3,
Sodium silicate; SSD, Saturated Surface Dry condition.
* Corresponding author. Tel.: þ91 674 2306353.
E-mail address: pdinakar@rediffmail.com (P. Dinakar).
environmental impacts. In these circumstances geopolymer con-
crete is found to be one of the better alternatives in terms of
reducing the global warming, as it can reduce the CO2 emissions
caused by cement industries by about 80% (Gartner, 2004). Geo-
polymer concrete (GPC) is a sustainable material which not only
utilises industrial wastes such as fly ash effectively but also serve as
a better alternative to ordinary Portland cement concrete (McLellan
et al., 2011). From the past decade or so geopolymer concrete is
certainly emerged as a novel construction material and has a huge
potential to become a prominent construction product of good
environmental sustainability (Chindaprasirt and Chalee, 2014; Sun
et al., 2013). Geopolymer concrete is a new form of concrete which
is produced by the alkali activation of material rich in aluminosil-
icates (Davidovits, 1991). Geopolymers binders can be produced
from variety of natural materials and industrial by-products like
metakaolin, fly ash, ground granulated blast furnace slag, red mud,
mine waste etc (Faten et al., 2013; Rahimah et al., 2015). Of these, fly
ash is a widely used source material due to its low cost, abundance
availability and greater potential for making geopolymers (Xu and
Deventer, 2000).
The alkaline activator solution mainly consists of soluble alkalis
that are usually of sodium or potassium based. Sodium hydroxide
(NaOH) in combination with sodium silicate (Na2SiO3) is the

http://dx.doi.org/10.1016/j.jclepro.2016.05.041
0959-6526/© 2016 Elsevier Ltd. All rights reserved.
118 P. Pavithra et al. / Journal of Cleaner Production 133 (2016) 117e125
commonly used alkaline activator to develop GPC (Kong and
Sanjayan, 2008). The common way to develop GPC is to dry mix
the solid constituents of 3 min followed by addition of liquid con-
stituents of the mixture and wet mixing for another 4 min (Hardjito
and Rangan, 2005), but Rattanasak and Chindaprasirt (2009)
noticed that mixing sequence has an effect on geopolymerization
and final compressive strength of the geopolymers. Also, it has been
reported that the molarity of NaOH solution influences the leaching
behaviour of aluminates and silicates from fly ash. Bakiri et al.
(2012) reported the influence of NaOH molarity and Na2SiO3 to
NaOH ratios on the compressive strength of fly ash based geo-
polymer concrete. Zarina et al. (2015) observed the effect of curing
temperature and time on the property of fly ash based geopolymer
pastes and noticed that curing temperature and time have affected
the geopolymer strength. Provis et al. (2012) found that modulus of
Na2SiO3 solution significantly affects the strength of fly ash based
geopolymer materials. Manjunath et al. (2011) observed the influ-
ence of activator solutions to fly ash ratios and NaOH molarities on
the compressive strength of fly ash based GPC. Hardjito et al. (2008)
described the effect of water to geopolymer solids ratios by mass on
the compressive strength of fly ash based GPC.
Development of geopolymer concrete requires suitable mix
design to attain its desired strength and workability. Despite of the
phenomenal research carried out in the area of geopolymer con-
crete there is only limited research available on its mix design, a
proper and more rational mix design method for GPC is still lacking.
Even though researchers like Anuradha et al. (2012), Ferdous et al.
(2013), etc proposed their own mix design methodologies; they are
all largely based by trial and error approach. Mix design and
proportioning of GPC become complex due to more variables being
involved in it (Montes et al., 2013) and there is no standard mix
design method available for designing GPC to date. Therefore, in
this paper an attempt has been made to present a new mix design
methodology for fly ash based GPC.
2. Review of mix design methods and limitations
A few mix design methodologies have been proposed earlier for
GPC. Of them all, Lloyd and Rangan (2010) were the first to propose
a mix design methodology for fly ash based geopolymer concrete.
According to this method, density of GPC has been assumed as
2400 kg/m3 and the total aggregates content was fixed at 80%. By
deducting the total aggregates content from the assumed density of
2400 kg/m3, the total mass of fly ash and alkaline activator solution
was obtained. Consequently, the fly ash content was determined
based on the activator solution to fly ash ratio. Further, individual
sodium silicate and sodium hydroxide content were determined
from the Na2SiO3/NaOH ratio employed. Finally, the designed
compressive strength and workability was determined by using
water to geopolymer solid ratios. The main thing lacking in this
method is that it doesn't take into consideration the specific gravity
of materials used. Anuradha et al. (2012) suggested a design pro-
cedure for different grade of GPC by using Indian standards. In this
method, fly ash content and activator solution to fly ash ratio was
selected based on the strength required and by keeping fine
aggregate percentage as constant. Later, correction to fine aggre-
gate percentage was performed based on its zone. The activator
solution content employed was observed to be excess for the cor-
responding strength reported. Ferdous et al. (2013) proposed a mix
design for fly ash based GPC by considering the concrete density
variability, specific gravity of the materials, air content, workability,
and the strength requirement. The significant issue that arises in
their design process could be the selection of activator solution to
fly ash ratio, and also in determining the exact activator solution
content with respect to the fly ash content. In GPC, alkaline solution
is a costly ingredient and from the economic design point of view,
use of alkaline solution must be minimised and also the desired
strength and workability has to be maintained. On account of
limited research conducted on mix design of GPC, there seems to be
no specific procedure which considers all the essential parameters.
Therefore, in this method an attempt has been made to propose a
mix design procedure which takes into account the aforesaid
drawbacks of the earlier proposed methods. Major emphasis has
been kept on the cost reduction without compromising on the
desired strength and workability.
3. Proposed method for designing GPC using fly ash
In this paper attempt has been made to propose mix design
methodology for fly ash based GPC in a rational way. As said earlier,
the activator solution is the costliest among the raw materials
involved in the production of GPC, and by fixing the activator
content the cost of the final GPC product can be considerably
brought down. Also, by doing this, flexibility in the design mixes
both on the strength requirement and desired activator solution
point of view can be rendered. The essential features of the pro-
posed method are the flexibility to select activator solution to fly
ash ratio required for specific strength and to estimate the probable
strength that can be achieved for certain activator solution to fly
ash ratio. Binder content is calculated based on the relationship
between activator solution content and activator solution to fly ash
ratio. In the proposed mix design methodology the materials vol-
ume and its specific gravity is also taken into account. Volume of
total aggregates is determined by using absolute volume method; it
considers the specific gravity of all the ingredients used. Then the
individual aggregate content is established from combined aggre-
gate grading curve. Provision is also made for enhancing the
workability of GPC. The procedure of the proposed mix design
methodology is outlined in the form of flow chart as depicted in
Fig. 1 and the step by step procedure is summarized as follows;
3.1. Fix the alkaline activator solution (AAS) content
In the mix proportioning of normal concrete, water content is
fixed based on the maximum size of the aggregate (IS 10262: 2009),
and the same procedure can be adopted in the case of GPC also for
fixing the AAS content. By following this method, the total water
content in the mix can be kept within the maximum water content
limits as prescribed in Table 1.
3.2. Selection of alkaline activator solution to fly ash ratio (AAS/FA)
(or) determination of strength
Generally when strength is considered as the principal criteria
then the alkaline activator solution to fly ash ratio corresponding to
the 28 day compressive strength can be chosen by adopting the
standard water to cement ratio curve of normal concrete as shown
in Fig. 2 which is as per ACI standards. For the mix designed for
specific AAS/FA ratio, then the minimum compressive strength that
has to be achieved at 28 days shall be determined from the corre-
lation between 28 day compressive strength and w/c ratio as
depicted in Fig. 2.
3.3. Calculation of binder content
Fly ash content was calculated using AAS/FA ratio and AAS
content. Let Bc be the binder content, then
Binder content ðBC Þ ¼ AAS content=ðAAS=FAÞ
 P. Pavithra et al. / Journal of Cleaner Production 133 (2016) 117e125 119

Fig. 1. Flow chart for proposed mix design methodology.

Table 1 Therefore, in the present study NaOH and Na2SiO3 were chosen as
Maximum water content per cubic metre of concrete (IS 10262: 2009). the activators.
Nominal maximum size of aggregate (mm) Maximum water content (kg/m3)
Let; Na2 SiO3 to NaOH ¼ R
10 208
20 186 Then; Mass of AAS ¼ Mass of ðNa2 SiO3 þ NaOHÞ
40 165
¼ Mass of ðR  NaOH þ NaOHÞ
¼ Mass of NaOH ðR þ 1Þ
Mass of NaOH ðMNaOH
Þ ¼ Mass of AAS=ðR þ 1Þ
3.4. Determination of activators content Mass of Na2 SiO3 MNa2 SiO3 ¼ R  MNaOH

From the literature, NaOH and Na2SiO3 were found to be the From the above relation, individual mass of NaOH and Na2SiO3
commonly used alkali activators (Lloyd and Rangan, 2010). can be determined.
120 P. Pavithra et al. / Journal of Cleaner Production 133 (2016) 117e125

80 3.7. Calculation of fine and coarse aggregate content

ACI Strength to water cement ratio
relationship of normal concrete The fine and coarse aggregate content was determined accord-
28 day Compressive Strength (MPa)

ing to combined aggregate grading as recommended by DIN 1045

60
standards (1988). Let the percentage of fine aggregate in the total
aggregate be x% and that of the coarse aggregate be y%. Various
sizes of coarse aggregates are used and are categorized as CA1, CA2
40 and CA3. Let percentage of CA1 mm size of aggregate be y1%,
CA2 mm size of aggregate be y2% and CA3 mm size of aggregate be
y3%. Then,

20 Mass of fine aggregate ðMFA
Þ ¼ ðx%  VA Þ  GFA  1000

Mass of CA1 aggregate MCA1
¼ ðy1 %  VA Þ  GCA1  1000
Mass of CA2 aggregate MCA2
¼ ðy2 %  VA Þ  GCA2  1000
Mass of CA3 aggregate MCA3 ¼ ðy3 %  VA Þ  GCA3  1000
0
0.3 0.4 0.5 0.6 0.7 0.8 0.9

w/c ratio where, GFA is the specific gravity of fine aggregate; GCA1 , GCA2 , and
GCA3 are the specific gravity of CA1 mm, CA2 mm, and CA3 mm
Fig. 2. Strength versus water to cement ratio curve. aggregate respectively.

3.8. Use of superplasticizer (SP)

3.5. Calculation of water content in AAS
Alkaline solution has the higher viscosity than the potable wa-
Water to geopolymer solid ratio is an important parameter ter. The alkaline solution when used for making concrete (GPC) it
which assist in the design of fly ash based GPC mixtures (Heah et al., was found to inhibit the concrete's workability, whereas when
2012). The total water present in the AAS should be determined to equal amount of water was used in ordinary concrete better
calculate the water to geopolymer solid ratio and the sum of the workability was observed. Therefore, attempts were made to
mass of the water present in the NaOH solution and Na2SiO3 so- improve the workability of GPC by adding some extra water, and it
lutions gives the total mass of water or water content of alkaline was noticed that the addition of extra water has detrimental effect
activator solution. on the strength and also bulging phenomenon in the specimens
Let, SNaOH and SNa2 SiO3 be the percentage of solids in NaOH and was observed. To avoid the addition of extra water, Naphthalene
Na2SiO3, respectively, then the water content is determined as based SP was used to improve the workability of GPC, and it was
follows; found that SP has the profound impact on the behaviour of fresh
Water Content ðWc Þ ¼ Mass of water in ðNaOH þ Na2 SiO3 Þ GPC without affecting much the strength and other properties.
Mass of water in NaOH ¼ MNaOH  ðSNaOH  MNaOH Þ Further, care has been taken to reduce the water demand by using
¼ MNaOH ð1  SNaOH Þ aggregates in their saturated surface dry (SSD) condition. From the


Mass of water in Na2 SiO3 ¼ MNa2 SiO3  SNa2 SiO3 
MNa2 SiO3 experimental observations it was found that the SP dosage was
¼ MNa2 SiO3 1  MNa2 SiO3 effective for the range between 0.8 and 1.5% of binder content.

3.9. Validation of strength attained with proposed mix design

3.6. Determination of total aggregates
The 28-day compressive strength obtained from testing has
The total aggregates content was determined as per the absolute been cross verified with the strength determined using the meth-
volume method. The volume of total aggregates include all the odology proposed in Section 3.2. If it satisfies the requirement, final
aggregates used in the study i.e. fine aggregate passing 4.75 mm development of GPC can be carried out or else the mix should be re-
and coarse aggregates passing 20 mm, 12.5 mm, and 6.3 mm in designed by changing the parameters.
different proportions. Let, the total volume of concrete is Vc, volume
of total aggregates is VTA, volume of binder is VB, volume of NaOH is 4. Verification of the mix methodology using experimental
VNaOH, volume of Na2SiO3 is VNa2 SiO3 , and volume of entrapped air data
be Va, then;
4.1. Preparation and testing of specimens
Volume of Concrete ðVc Þ ¼ VTA þ VB þ VNaOH þ VNa2 SiO3 þ Va
In order to validate the mix design proposed, laboratory ex-
Where, VB ¼ Bc/GB; periments have been conducted.
VNaOH ¼ MNaOH/GNaOH; Based on the mortar trial mix results, NaOH molarity and
VNa2 SiO3 ¼ MNa2 SiO3 =GNa2 SiO3 ; Va assumed as 2% Na2SiO3 to NaOH ratio were fixed at 16 M and 1.5, respectively. GPC
GB, GNaOH, and GNa2 SiO3 are the specific gravities of binder, NaOH, specimens were cast for different AAS/FA ratios such as 0.4, 0.5, 0.6,
and Na2SiO3 respectively. 0.7, and 0.8. NaOH solution was prepared one day in advance to
account for complete dissolution of crystals and dissipation of heat
Let us consider 1cubic metre concrete, then; liberated. The mix proportions as shown in Table 2 were employed
for making the GPC specimens. The fly ash used was classified as
0:98 ¼ VTA þ VB þ VNaOH þ VNa2 SiO3 Class F fly ash as per the ASTM specifications and its chemical

VTA ¼ 0:98  ðBc =GB Þ þ ðMNaOH =GNaOH Þ composition was shown in Table 3. Crushed granite stones with

 maximum size of 20 mm were used as coarse aggregates, and a
þ MNa2 SiO3 GNa2 SiO3  f1=1000g
good quality, well-graded river sand categorized as Zone-II with
 P. Pavithra et al. / Journal of Cleaner Production 133 (2016) 117e125 121

Table 2
Mix proportion used in the study.

Mix AAS/FA Fly ash Kg/m3 NaOH Kg/m3 Na2SiO3 Kg/m3 Aggregates (kg/m3) Water/Geopolymer Solid SP kg/m3

20 mm 12.5 mm 6.3 mm Fine Aggregate

1 0.4 500 80 120 465 538 318 320 0.21 6

2 0.5 400 80 120 500 578 341 344 0.26 4
3 0.6 333 80 120 523 605 357 360 0.30 3.2
4 0.7 286 80 120 540 624 369 371 0.34 e
5 0.8 250 80 120 552 638 377 380 0.37 e

Table 3
Chemical composition of fly ash.

Oxide SiO2 Al2O3 Fe2O3 CaO Na2O K2O MgO SO3 LOI

Wt (%) 61.89 28.05 4.11 0.87 0.40 0.82 0.38 1.32 0.49

maximum grain size of 4.75 mm were used as fine aggregates,

respectively. The coarse aggregates used consist of various particle
sizes passing 20 mm, 12.5 mm and 6.3 mm size sieves in various
proportions as elaborated below.
In order to verify the mix design procedure, a sample design of
GPC with AAS/FA ratio of 0.5 is considered as an example. The
important parameters considered in the mix consists of percentage
of solids in NaOH is 45.5%, percentage of solids in Na2SiO3 is 34.5%,
specific gravity of fly ash is 2.2, NaOH is 1.451, Na2SiO3 is 1.35. The
specific gravity of the aggregates such as 20 mm passing, 12.5 mm
passing, 6.3 mm passing, and 4.75 mm (sand) passing is 2.73, 2.76,
2.61, and 2.63, respectively. The sample design procedure is
explained in an example.
For each mix type, a set of 3 cubes of size 10  10  10 cm each
for determining 28 day and 90 day compressive strength were cast.
The mixing sequence employed consists of dry mixing of the solid
components in the laboratory pan mixer for 3 min and then
continued mixing for another 3 min by adding AAS. After ensuring
proper mixing of all the components Naphthalene based super-
plasticizer was added and mixing was continued for further 4 min.
Wet mixing time was observed to be very crucial for GPC strength
development. Care has been taken to ensure proper mixing of AAS
with fly ash. The workability of GPC was determined using slump
Fig. 3. Mixing and curing of GPC.
cone test as per ASTM C 143 (2005). Immediately after casting, the
specimens were covered with a polythene film and then kept in
better strength, workability and economy. Moreover, at AAS con-
oven at a constant temperature of 60  C for a period of 24 h as
tent of 200 kg/m3, the water content present in the AAS found to be
shown in Fig. 3. At the end of the curing period the specimens were
within the maximum water content limits given in Table 1 for
removed from oven and allowed to cool at room temperature
20 mm maximum aggregate size case.
before demoulding. Later, the specimens were left to air dry at at-
mospheric temperature until the day of testing. Compressive STEP 2: Determination of Strength
strength test was carried out at the age of 28 and 90 days, and the
average value of the three specimens was considered. From Fig. 2, for AAS/FA ratio of 0.5, the minimum 28 day
In order to verify the mix design procedure, a sample design of compressive strength that has to be obtained is 38 MPa.
GPC with AAS/FA ratio of 0.5 is considered as an example. The STEP 3: Calculation of Binder Content
important parameters considered in the mix consists of percentage
of solids in NaOH is 45.5%, percentage of solids in Na2SiO3 is 34.5%,
Binder content ðBC Þ ¼ AAS content=ðAAS=FAÞ
specific gravity of fly ash is 2.2, NaOH is 1.451, Na2SiO3 is 1.35. The BC ¼ 200=0:5 ¼ 400 kg=m3
specific gravity of the aggregates such as 20 mm passing, 12.5 mm STEP 4: Calculation of individual activator solution contents
passing, 6.3 mm passing, and 4.75 mm (sand) passing is 2.73, 2.76,
2.61, and 2.63, respectively. The sample design procedure is For all the mixes the Na2SiO3 and NaOH ratio employed was 1.5,
explained as follows; and R shall be taken as 1.5.

4.2. Mix methodology verification using an example Mass of AAS ¼ Mass of NaOH ð1:5 þ 1Þ
Mass of NaOH ðMNaOH Þ ¼ Mass of AAS=2:5
STEP 1: Fix the Alkaline Activator Solution (AAS) Content ¼ 200=2:5

¼ 80 kg=m3
Mass of Na2 SiO3 MNa2 SiO3 ¼ 1:5  MNaOH
From the trials carried out in the laboratory it was found that at
¼ 1:5  80 ¼ 120 kg=m3
an AAS content of 200 kg/m3 GPC can be developed effectively with
122 P. Pavithra et al. / Journal of Cleaner Production 133 (2016) 117e125

100
STEP 5: Calculation of Water Content in AAS
Grading curve used for GPC
Standard DIN 'A' grading curve
Mass of water in NaOH ¼ MNaOH ð1  SNaOH Þ
80
¼ 80 ð1  0:455Þ Aggregate percentage fraction used
¼ 80 ð0:545Þ 20 mm - 28%
12.5 mm - 32%
¼ 43:6 kg=m3
60 6.3 mm - 20%

% passing
Mass of water in Na2 SiO3 ¼ MNa2 SiO3 1  SNa2 SiO3 Fine - 20%
¼ 120 ð1  0:345Þ
¼ 120 ð0:655Þ 40
¼ 78:6 kg=m3
Total Water Content ðWc Þ in the mix ¼ Mass of water in
ðNaOH þ Na2 SiO3 Þ 20

¼ 43:6 þ 78:6
¼ 122:2 kg=m3
0
From the above calculations it is found that 16 M NaOH solutions 0.1 1 10
Particle size (log scale) (mm)
prepared for the mix consists of 36.4 kg solids dissolved in 43.6 kg
of water, and the sodium silicate gel used in the mix consists of Fig. 4. Combined aggregate grading curve.
78.6 kg of water out of 120 kg solution. The total water content in
the mix is thus found to be 122.2 kg per cubic metre of concrete.
The total solid content which includes the fly ash, solids in NaOH,
and Na2SiO3 in the mix contains 477.8 kg per cubic metre of con- STEP 8: Superplasticizer (SP) Dosage
crete. Thus, the water to geopolymer solid ratio is obtained as 0.26.
Based on the experimental observations in the laboratory, SP
STEP 6: Determination of Total Aggregates dosage of 1% of binder content is found to be suitable to improve
the workability and the same has been followed in this case.
The volume of total aggregates (VTA) is obtained by using the
absolute volume method as follows: SP Dosage ¼ 1%  400 ¼ 4 kg=m3

VTA ¼ 0:98  ðBc =GB Þ þ ðMNaOH =GNaOH Þ


þ MNa2 SiO3 MNa2 SiO3  f1=1000g STEP 9: Validation of Strength Achieved
¼ 0:98  ½fð400=2:2Þ þ ð80=1:4506Þ þ ð120=1:35Þg
Compressive strength tests were conducted on the cubes cast in
 f1=1000g
the laboratory by using the mix design proposed above. From the
¼ 0:98  0:326 ¼ 0:654 m3 tests, the 28 day compressive strength obtained was 45.95 MPa. The
strength obtained found to be greater than the corresponding
strength of 37.69 MPa which was required as per Fig. 2. As the
STEP 7: Calculation of Fine and Coarse Aggregate Content designed mix satisfies the strength requirement, the final devel-
opment of GPC can be made by employing the above design steps.
Combined aggregate grading to match the standard combined
grading curve as recommended by DIN 1045 (1988) standard was 5. Experimental results and discussion
utilized. Coarse aggregates passing 20 mm, 12.5 mm, 6.3 mm size
sieves, and fine aggregates passing 4.75 mm size sieve were used in Tests were conducted on different GPC mixes with various AAS/
various proportions to meet the standard grading curve of DIN ‘A’ FA ratios and the results showing slump value and compressive
which is as shown in Fig. 4. The aggregates proportion comprising strengths were tabulated as shown in Table 4. From the table, it can
of 28% of 20 mm passing, 32% of 12 mm passing, 20% of 6 mm be observed that slump value increased with the increase in the
passing, and 20% of 4.75 mm passing, has been adopted to meet the activator solution to fly ash ratio. Similar trend can be observed
requirements of DIN ‘A’ grading curve. The proportions of each with the normal concrete, where slump increases with increase in
fractions of aggregates used are also shown in Fig. 4. water to cement ratio (Alawode and Idowu, 2011). Further, it was
Massof fine aggregateðMFA Þ ¼ ð20%VA ÞGFA 1000 observed that the compressive strengths obtained for the designed
GPC mixes with various AAS/FA ratios were found to be higher than
¼ ð20%0:654Þ2:631000
the corresponding strengths derived from the strength vs. w/c ratio
¼ 344 kg=m3 curve of ACI standards for normal concrete as shown in Fig. 2.
Massof 20mmaggregate ðM20 Þ ¼ ð28%VA ÞG20 1000 However, the alkaline activator solution to fly ash ratio does not
exactly fit with the ACI proposed strength vs. water to cement ratio
¼ ð28%0:654Þ2:731000
¼ 499:92 kg=m3
Table 4
Massof 12:5mm aggregateðM12:5 Þ ¼ ð32%VA ÞG12:5 1000 Properties of GPC.
¼ ð32%0:654Þ2:761000
AAS/FA Slump (mm) 28 day strength (MPa) 90 day strength (MPa)
¼ 577:61 kg=m3 0.4 35 53.56 55.33
Massof 6:3mm aggregate ðM6:3 Þ ¼ ð20%VA ÞG6:3 1000 0.5 60 45.95 47.49
0.6 80 37.12 39.96
¼ ð20%0:654Þ2:611000 0.7 110 33.41 36.85
¼ 341:38 kg=m3 0.8 Collapse 23.45 28.26
 P. Pavithra et al. / Journal of Cleaner Production 133 (2016) 117e125 123

60 curve. In order to rationalize the design mix, comparisons of the

strengths obtained were made with the modified ACI strength vs.
R2 = 0.934
28 day compressive strength (MPa)

w/c ratio proposed by Dinakar et al. (2013) as shown in Fig. 5. In the

50 28 day compressive strength = 20.352 (AAS/FA) -1.119
design mix, AAS/FA ratio has been treated as w/c ratio. Comparisons
were made between the compressive strengths determined from
the designed GPC mixes and the strengths determined from
40
modified ACI relationship of normal concrete shown in Fig. 5. The
results revealed that the strengths obtained in the case of GPC
30
design mixes were in line with the corresponding OPC concretes.
It has also been observed from the experimental results that GPC
mixes have followed similar trend as that of OPC concrete mixes.
Normal concrete
20 (ACI relationship)
Like OPC concretes GPCs shown decrease in the compressive
GPC relationship strengths with the increase in AAS/FA ratio (water to cement ratio
in case of OPCs).
10 Further, it has been found that, with the decrease in the AAS/FA
0.3 0.4 0.5 0.6 0.7 0.8 0.9
ratio the compressive strength increased for both 28 days and 90
w/c (or) AAS/FA days, as shown in Table 4. The 28 day strengths of GPC mixes were
found to be varied between 23.45 and 53.56 MPa, and that of 90 day
Fig. 5. Comparison of 28 day strengths.

Fig. 6. SEM images of fly ash based GPC for different AAS/FA (a) 0.4 (b) 0.5 (c) 0.6 (d) 0.7 (e) 0.8.
124 P. Pavithra et al. / Journal of Cleaner Production 133 (2016) 117e125
strengths were found to be varied between 28.26 and 55.33 MPa. As
such, not much increase in the strength was observed between 28
days and 90 days tested samples, and the 90-day strengths of GPC
mixtures were found to be around 103e120% of the 28-day
strength. This increase may be due to the continued polymerisation
at the room temperature (Amol et al., 2014). Also, it was noticed
that, significant strength gain with age was observed for concretes
with high activator solution to fly ash ratio. This could be due to the
excess solution present in the system which hinders the polymer-
isation process in the initial stage (Heah et al., 2012). Further, it was
observed from the studies that the strengths of GPCs increased with
age for all the GPC mixes made with various AAS/FA ratios.
The compressive strength developed in GPC has been found to
be more sensitive to the liquid in the mix design (Albitar et al.,
2015). High amount of liquid content than the solids in the
mixture leads to the decrease in the strength because of the
reduced contact between the activating solution and the reacting
material. This reduced contact has been found to be due to the large
volume occupation of liquids (He et al., 2013). To better understand
these facts, SEM images of GPC obtained for different solutions to
binder ratio were shown in Fig. 6. Unreacted fly ash particles were
clearly seen in the samples (shown with arrow marks). More vol-
ume of unreacted fly ash particles can be observed with the in-
crease in the AAS/FA ratio. Several phases like unreacted fly ash
particles, particles attacked by activator solution, reaction products,
etc., can be observed in the geopolymer matrix shown in Fig. 6, and
it is in agreement with the earlier observation reported by Jimenez
et al. (2005). The larger precipitations have been observed for GPC
with activator solution to fly ash ratio of 0.4, and gradual decrease
in the precipitations was noticed with the increase in the activator
solution. Similar effect was noticed earlier by Heah et al. (2012). On
further examination of SEM images of various mixes it was noticed
that increase in the activator solution content limits the contact
between the fly ash particles and activator solution and it could be
the reason for the decrease in compressive strength. Further, it was
also observed that unreacted fly ash particles present in the higher
solution systems were covered with some unknown films which
possibly could have hindered the polymerisation process (Arioz
and Koçkar, 2013).
The overall results showed that excellent compressive strengths
can be achieved by following the proposed mix design method. All
GPC mixes have met their strength requirements with respective to
the modified ACI strength to water cement ratio curve, for different
activator solution to fly ash ratios. It can also be seen that GPC of
desired strength can be obtained by using the proposed mix design
methodology. Compressive strengths ranging from 23 to 53 MPa
were obtained by using the proposed mix design methodology.
Hence, the proposed mix design method can be employed to design
the fly ash based GPC efficiently and effectively for regular struc-
tural works.
6. Conclusions
A rational mix design approach for fly ash based GPC has been
introduced. A review on the earlier proposed mix designs shows
that they all depend mainly on the AAS content. As AAS is the
costliest ingredient of all, providing flexibility in fixing the AAS
content is very advantageous from the economy point of view. The
findings of this study suggest that, using the proposed method GPC
can be produced for a specific strength by employing the corre-
sponding AAS/FA ratio obtained from the modified ACI strength vs.
w/c ratio curve. GPC can also be produced for a specific AAS/FA ratio
to achieve the corresponding strength. Using the proposed
methodology, fly ash based GPC of strengths ranging from 23 to
53 MPa at varying activator solution to fly ash ratio can be devel-
oped. By strictly following the proposed steps the required GPCs
can be produced effectively and efficiently. From the experimental
investigations it has been found that, GPC follow similar trend to
that of normal concrete in the strength aspect where the strength
decreases with the increase in the fluid content.
Acknowledgement
The authors are thankful to National Aluminium Company
Limited (NALCO), (NBC/R&D/3415/2014) Bhubaneswar for funding
this research work. The financial support is greatly acknowledged.
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