Accepted Manuscript

A mix design procedure for geopolymer concrete with fly ash

P. Pavithra, Former PG Student, M. Srinivasula Reddy, Research Scholar, Pasla

Dinakar, Associate Professor, B. Hanumantha Rao, Assistant Professor, B.K.
Satpathy, A.N. Mohanty

PII: S0959-6526(16)30496-6
DOI: 10.1016/j.jclepro.2016.05.041
Reference: JCLP 7223

To appear in: Journal of Cleaner Production

Received Date: 20 October 2015

Revised Date: 7 May 2016
Accepted Date: 7 May 2016

Please cite this article as: Pavithra P, Srinivasula Reddy M, Dinakar P, Hanumantha Rao B, Satpathy B,
Mohanty A, A mix design procedure for geopolymer concrete with fly ash, Journal of Cleaner Production
(2016), doi: 10.1016/j.jclepro.2016.05.041.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
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 ACCEPTED MANUSCRIPT

Absolute Volume Method

100 60
AAS = 200 kg/m3

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Grading curve used for GPC

28 day compressive strength (MPa)

Standard DIN 'A' grading curve R2 = 0.934

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80
(Constant for all mixes) 50 28 day compressive strength = 20.352 (AAS/FA) -1.119

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Aggregate percentage fraction used
20 mm - 28%

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12.5 mm - 32%

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60 6.3 mm - 20% 40
% passing

Fine - 20%

M
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40 30

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Normal concrete
20 (ACI relationship)
20

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GPC relationship

AC
10
0 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0.1 1
Particle size (log scale) (mm)
10
NaOH = 80 kg/m3 w/c (or) AAS/FA
Na2SiO3 = 120 kg/m3
 ACCEPTED MANUSCRIPT
A mix design procedure for geopolymer concrete with fly ash

P Pavithra 1, M Srinivasula Reddy2, Pasla Dinakar#3, B Hanumantha Rao4, B K Satpathy5, A N Mohanty6

1
Former PG Student, 2Research Scholar, School of Infrastructure, Indian Institute of Technology, Bhubaneswar,
Odisha 751013, India
3,
Associate Professor, 4Assistant Professor, School of Infrastructure, Indian Institute of Technology,

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Bhubaneswar, Odisha 751013, India
5,6
National Aluminium Company Limited (NALCO), Bhubaneswar 751013, India

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Abstract

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Effective promotion of GPC is required in order to minimize the environment threat due to
fly ash waste disposal and reduce cement consumption. To achieve this, specific mix design
procedure for development of GPC is essential. Therefore, efforts have been made in this

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paper to develop a mix design methodology for GPC with the main focus on achieving better
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compressive strength in an economical 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
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DIN standards, have been employed for conducting experimental investigation. Correlation
between the alkaline activator solution to binder ratios and 28 day compressive strength has
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been investigated to propose conceptual mix design method for GPC in a rational way. Mix
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design is proposed for various AAS/FA ratios ranging from 0.4 to 0.8, and the 28 day
compressive strength as high as 54 MPa has been noticed. The design methodology proposed
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has been given step-wise and the same has been verified with the help of an example in this
paper.
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Keywords: Activator solution; Compressive strength; Fly ash; Geopolymer concrete; Mix
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design.

#Corresponding author. Tel. No. +91 674 2306353 Email address: pdinakar@rediffmail.com

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Abbreviations used

AAS - Alkaline Activator Solution

AAS/FA - Alkaline Activator Solution to Fly Ash

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GPC - GeoPolymer Concrete

NaOH - Sodium hydroxide

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Na2SiO3 - Sodium silicate

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SSD - Saturated Surface Dry condition

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AN
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D
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1. Introduction

Nowadays, the increase in the people’s attention on the conservation of natural

resources and minimization of environment depletion has led to look at the alternatives to

accustomed construction materials. Currently, ordinary Portland cement based concrete is

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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 (USGS, 2014). The major problems

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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

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same time the disposal of industrial wastes such as fly ash, ground granulated blast furnace

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slag, mine waste, red mud etc, has become a big problem, it requires large areas of useful
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land and also has huge impact on the environment. Therefore, the need is emanated from

further investigation into safe waste disposal and investigation into alternative to cement
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products with reduced environmental impacts. In these circumstances geopolymer concrete is

found to be one of the better alternatives in terms of reducing the global warming, as it can
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reduce the CO2 emissions caused by cement industries by about 80% (Gartner, 2004).
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Geopolymer concrete (GPC) is a sustainable material which not only utilises industrial wastes
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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
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emerged as a novel construction material and has a huge potential to become a prominent
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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 aluminosilicates (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 ;

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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

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(Na2SiO3) is the commonly used alkaline activator to develop GPC (Kong et al., 2008). The

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common way to develop GPC is to dry mix the solid constituents of three minutes followed

by addition of liquid constituents of the mixture and wet mixing for another four minutes

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(Hardjito and Rangan, 2005), but Rattanasak and Chindaprasirt (2009) noticed that mixing

sequence has an effect on geopolymerization and final compressive strength of the

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geopolymers. Also, it has been reported that the molarity of NaOH solution influences the
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leaching behaviour of aluminates and silicates from fly ash. Al Bakiri et al. (2012) reported
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the influence of NaOH molarity and Na2SiO3 to NaOH ratios on the compressive strength of

fly ash based geopolymer concrete. Zarina et al. (2015) observed the effect of curing
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temperature and time on the property of fly ash based geopolymer pastes and noticed that
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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
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geopolymer materials. Manjunath et al. (2011) observed the influence of activator solutions
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to fly ash ratios and NaOH molarities on the compressive strength of fly ash based GPC.
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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 concrete 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
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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

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for fly ash based GPC.

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2. Review of mix design methods and limitations

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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

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based geopolymer concrete. According to this method, density of GPC has been assumed as
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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
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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
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hydroxide content were determined from the Na2SiO3/NaOH ratio employed. Finally, the
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designed compressive strength and workability was determined by using water to geopolymer
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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 procedure
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for different grade of GPC by using Indian standards. In this method, fly ash content and
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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 aggregate percentage was

performed based on its zone. The activator solution content employed was observed to be

excess for the corresponding 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

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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

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maintained. On account of limited research conducted on mix design of GPC, there seems to

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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

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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.

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3. Proposed method for designing GPC using fly ash

In this paper attempt has been made to propose mix design methodology for fly ash
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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
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of the final GPC product can be considerably brought down. Also, by doing this, flexibility in
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the design mixes both on the strength requirement and desired activator solution point of
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view can be rendered. The essential features of the proposed method are the flexibility to

select activator solution to fly ash ratio required for specific strength and to estimate the
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probable strength that can be achieved for certain activator solution to fly ash ratio. Binder
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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

volume 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

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aggregate 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

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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

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the case of GPC also for fixing the AAS content. By following this method, the total water

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content in the mix can be kept within the maximum water content limits as prescribed in

Table 1.

3.2
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Selection of Alkaline Activator Solution to Fly Ash Ratio (AAS/FA) (OR)
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Determination of Strength

Generally when strength is considered as the principal criteria then the alkaline
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activator solution to fly ash ratio corresponding to the 28 day compressive strength can be
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chosen by adopting the standard water to cement ratio curve of normal concrete as shown in
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the 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
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determined from the correlation between 28 day compressive strength and w/c ratio as

depicted in Fig. 2.
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AC

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 (BC) = AAS content / (AAS/FA)

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3.4 Determination of Activators Content

From the literature, NaOH and Na2SiO3 were found to be the commonly used alkali

activators (Lloyd and Rangan, 2010). Therefore, in the present study NaOH and Na2SiO3

were chosen as the activators.

Let, Na2SiO3 to NaOH = R

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Then, Mass of AAS = Mass of (Na2SiO3 + NaOH)

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= Mass of (R x NaOH + NaOH)

= Mass of NaOH (R + 1)

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Mass of NaOH (MNaOH) = Mass of AAS/ (R+1)

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Mass of Na2SiO3 (MNa2SiO3) AN = R x MNaOH

From the above relation, individual mass of NaOH and Na2SiO3 can be determined.

3.5 Calculation of Water Content in AAS

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Water to geopolymer solid ratio is an important parameter which assist in the design
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of fly ash based GPC mixtures (Heah et al., 2012). The total water present in the AAS should
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be determined to calculate the water to geopolymer solid ratio and the sum of the mass of the

water present in the NaOH solution and Na2SiO3 solutions gives the total mass of water or
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water content of alkaline activator solution.

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Let, SNaOH and SNa2SiO3 be the percentage of solids in NaOH and Na2SiO3,
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respectively, then the water content is determined as follows;

Water Content (Wc) = Mass of water in (NaOH + Na2SiO3)

Mass of water in NaOH = MNaOH – (SNaOH x MNaOH)

= MNaOH (1 - SNaOH)

Mass of water in Na2SiO3 = MNa2SiO3 – (SNa2SiO3 x MNa2SiO3)

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= MNa2SiO3 (1 - MNa2SiO3)

3.6 Determination of Total Aggregates

The total aggregates content was determined as per the absolute volume method. The

volume of total aggregates include all the aggregates used in the study i.e. fine aggregate

passing 4.75mm and coarse aggregates passing 20mm, 12.5mm, and 6.3mm in different

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proportions. Let, the total volume of concrete is Vc, volume of total aggregates is VTA,

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volume of binder is VB, volume of NaOH is VNaOH, volume of Na2SiO3 is VNa2SiO3, and

volume of entrapped air be Va, then;

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Volume of Concrete (Vc) = VTA + VB + VNaOH + VNa2SiO3 + Va

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Where, VB = Bc/GB;
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VNaOH = MNaOH/GNaOH;

VNa2SiO3 = MNa2SiO3/GNa2SiO3; Va assumed as 2%

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GB, GNaOH, and GNa2SiO3 are the specific gravities

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of binder, NaOH, and Na2SiO3 respectively.

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Let us consider 1cubic meter concrete, then;

0.98 = VTA + VB + VNaOH + VNa2SiO3

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VTA = 0.98 – [{(Bc/GB) + (MNaOH/GNaOH) +

(MNa2SiO3/GNa2SiO3)} x{1/1000}]
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3.7 Calculation of Fine and Coarse Aggregate Content

The fine and coarse aggregate content was determined according to combined

aggregate grading as recommended by DIN 1045 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 and CA3. Let percentage of

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CA1 mm size of aggregate be y1%, CA2 mm size of aggregate be y2% and CA3 mm size of

aggregate be y3%. Then,

Mass of fine aggregate (MFA) = (x% x VA) x GFA x 1000

Mass of CA1 aggregate (MCA1) = (y1% x VA) x GCA1 x 1000

Mass of CA2 aggregate (MCA2) = (y2% x VA) x GCA2 x 1000

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Mass of CA3 aggregate (MCA3) = (y3% x VA) x GCA3 x 1000

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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 aggregate respectively.

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3.8 Use of Superplasticizer (SP)

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Alkaline solution has the higher viscosity than the potable water. The alkaline
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solution when used for making concrete (GPC) it was found to inhibit the concrete’s

workability, whereas when equal amount of water was used in ordinary concrete better
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workability was observed. Therefore, attempts were made to improve the workability of GPC

by adding some extra water, and it was noticed that the addition of extra water has
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detrimental effect on the strength and also bulging phenomenon in the specimens was
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observed. To avoid the addition of extra water, Naphthalene based SP was used to improve
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the workability of GPC, and it was found that SP has the profound impact on the behaviour of

fresh GPC without affecting much the strength and other properties. Further, care has been
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taken to reduce the water demand by using aggregates in their saturated surface dry (SSD)
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condition. From the experimental observations it was found that the SP dosage was effective

for the range between 0.8 and 1.5% of binder content.

3.9 Validation of strength attained with proposed mix design

The 28-day compressive strength obtained from testing has been cross verified with

the strength determined using the methodology proposed in section 3.2. If it satisfies the

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requirement, final development of GPC can be carried out or else the mix should be re-

designed by changing the parameters.

4. Verification of the mix methodology using experimental data

4.1 Preparation and testing of specimens

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In order to validate the mix design proposed, laboratory experiments have been conducted.

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Based on the mortar trial mix results, NaOH molarity and Na2SiO3 to NaOH ratio were fixed

at 16M and 1.5, respectively. GPC specimens were cast for different AAS/FA ratios such as

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0.4, 0.5, 0.6, 0.7, and 0.8. NaOH solution was prepared one day in advance to account for

complete dissolution of crystals and dissipation of heat liberated. The mix proportions as

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shown in Table 2 were employed for making the GPC specimens. The fly ash used was
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classified as Class F fly ash as per the ASTM specifications and its chemical composition
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was shown in Table 3. Crushed granite stones with maximum size of 20 mm were used as

coarse aggregates, and a good quality, well-graded river sand categorized as Zone-II with
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maximum grain size of 4.75 mm were used as fine aggregates, respectively. The coarse
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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.

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In order to verify the mix design procedure, a sample design of GPC with AAS/FA
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ratio of 0.5 is considered as an example. The important parameters considered in the mix
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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 20mm passing, 12.5mm passing, 6.3mm passing, and 4.75mm (sand)

passing is 2.73, 2.76, 2.61, and 2.63, respectively. The sample design procedure is

explained in an example.

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For each mix type, a set of 3 cubes of size 10 x 10 x 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 three minutes and then

continued mixing for another three minutes by adding AAS. After ensuring proper mixing of

all the components Naphthalene based superplasticizer was added and mixing was continued

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for further four minutes. Wet mixing time was observed to be very crucial for GPC strength

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development. Care has been taken to ensure proper mixing of AAS with fly ash. The

workability of GPC was determined using slump cone test as per ASTM C 143 (2005).

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Immediately after casting, the specimens were covered with a polythene film and then kept in

oven at a constant temperature of 60°C for a period of 24 hours as shown in Fig. 3. At the end

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of the curing period the specimens were removed from oven and allowed to cool at room
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temperature before demoulding. Later, the specimens were left to air dry at atmospheric
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temperature until the day of testing. Compressive strength test was carried out at the age of

28 and 90 days, and the average value of the three specimens was considered.
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In order to verify the mix design procedure, a sample design of GPC with AAS/FA
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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%,

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specific gravity of fly ash is 2.2, NaOH is 1.451, Na2SiO3 is 1.35. The specific gravity of the
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aggregates such as 20mm passing, 12.5mm passing, 6.3mm passing, and 4.75mm (sand)
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passing is 2.73, 2.76, 2.61, and 2.63, respectively. The sample design procedure is

explained as follows;

4.2 Mix methodology verification using an example

STEP 1: Fix the Alkaline Activator Solution (AAS) Content

From the trials carried out in the laboratory it was found that at an AAS content of

200 kg/m3 GPC can be developed effectively with better strength, workability and economy.
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Moreover, at AAS content of 200 kg/m3, the water content present in the AAS found to be

within the maximum water content limits given in Table 1 for 20 mm maximum aggregate

size case.

STEP 2: Determination of Strength

From Fig. 2, for AAS/FA ratio of 0.5, the minimum 28 day compressive strength that

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has to be obtained is 38 MPa.

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STEP 3: Calculation of Binder Content

Binder content (BC) = AAS content / (AAS/FA)

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BC = 200 / 0.5 = 400 kg/m3

STEP 4: Calculation of individual activator solution contents

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For all the mixes the Na2SiO3 and NaOH ratio employed was 1.5, and R shall be taken
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as 1.5.
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Mass of AAS = Mass of NaOH (1.5 + 1)

Mass of NaOH (MNaOH) = Mass of AAS/2.5

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= 200/2.5 = 80 kg/m3
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Mass of Na2SiO3 (MNa2SiO3) = 1.5 x MNaOH

= 1.5 x 80 = 120 kg/m3

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STEP 5: Calculation of Water Content in AAS

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Mass of water in NaOH = MNaOH (1 - SNaOH)

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= 80 (1- 0.455)

= 80 (0.545) = 43.6 kg/m3

Mass of water in Na2SiO3 = MNa2SiO3 (1 - SNa2SiO3)

= 120 (1 – 0.345)

= 120 (0.655) = 78.6 kg/m3

Total Water Content (Wc) in the mix = Mass of water in (NaOH + Na2SiO3)
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= 43.6 + 78.6 = 122.2 kg/m3

From the above calculations it is found that 16M NaOH solutions 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 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 meter of concrete. The total solid content which

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includes the fly ash, solids in NaOH, and Na2SiO3 in the mix contains 477.8 kg per cubic

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meter of concrete. Thus, the water to geopolymer solid ratio is obtained as 0.26.

STEP 6: Determination of Total Aggregates

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The volume of total aggregates (VTA) is obtained by using the absolute volume

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method as follows: AN
VTA = 0.98 – [{(Bc/GB) + (MNaOH/GNaOH) +

(MNa2SiO3/MNa2SiO3)} x {1/1000}]
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= 0.98 – [{(400/2.2) + (80/1.4506) +

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(120/1.35)} x {1/1000}]
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= 0.98 – 0.326 = 0.654 m3

STEP 7: Calculation of Fine and Coarse Aggregate Content

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Combined aggregate grading to match the standard combined grading curve as

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recommended by DIN 1045 (1988) standard was utilized. Coarse aggregates passing 20 mm,
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12.5 mm, 6.3 mm size sieves, and fine aggregates passing 4.75mm size sieve were used in

various proportions to meet the standard grading curve of DIN ‘A’ which is as shown in the

Fig. 4. The aggregates proportion comprising of 28% of 20 mm passing, 32% of 12 mm

passing, 20% of 6 mm passing, and 20% of 4.75 mm passing, has been adopted to meet the

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requirements of DIN ‘A’ grading curve. The proportions of each fractions of aggregates used

are also shown in Fig. 4.

Mass of fine aggregate (MFA) = (20% x VA) x GFA x 1000

= (20% x 0.654) x 2.63 x 1000

= 344 kg/m3

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Mass of 20mm aggregate (M20) = (28% x VA) x G20 x 1000

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= (28% x 0.654) x 2.73 x 1000

= 499.92 kg/m3

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Mass of 12.5mm aggregate (M12.5) = (32% x VA) x G12.5 x 1000

= (32% x 0.654) x 2.76 x 1000

U= 577.61 kg/m3
AN
Mass of 6.3mm aggregate (M6.3) = (20% x VA) x G6.3 x 1000
M

= (20% x 0.654) x 2.61 x 1000

= 341.38 kg/m3
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STEP 8: Superplasticizer (SP) Dosage

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Based on the experimental observations in the laboratory, SP dosage of 1% of binder

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content is found to be suitable to improve the workability and the same has been followed in

this case.
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SP Dosage = 1% x 400 = 4 kg/m3

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STEP 9: Validation of Strength Achieved

Compressive strength tests were conducted on the cubes cast in the laboratory by

using the mix design proposed above. From the 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 designed mix satisfies the

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strength requirement, the final development of GPC can be made by employing the above

design steps.

5. Experimental Results and Discussion

Tests were conducted on different GPC mixes with various AAS/FA ratios and the

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results showing slump value and compressive strengths were tabulated as shown in Table 4.

From the table, it can be observed that slump value increased with the increase in the

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activator solution to fly ash ratio. Similar trend can be observed with the normal concrete,

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where slump increases with increase in water to cement ratio (Alawode and Idowu, 2011).

Further, it was observed that the compressive strengths obtained for the designed GPC mixes

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with various AAS/FA ratios were found to be higher than the corresponding strengths derived
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from the strength vs. w/c ratio curve of ACI standards for normal concrete as shown in Fig. 2.

However, the alkaline activator solution to fly ash ratio does not exactly fit with the
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ACI proposed strength vs. water to cement ratio curve. In order to rationalize the design mix,
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comparisons of the strengths obtained were made with the modified ACI strength vs. w/c
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ratio proposed by Dinakar et al., (2013) as shown in the Fig. 5. In the design mix, AAS/FA

ratio has been treated as w/c ratio. Comparisons were made between the compressive
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strengths determined from the designed GPC mixes and the strengths determined from

modified ACI relationship of normal concrete shown in the Fig. 5. The results revealed that
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the strengths obtained in the case of GPC design mixes were in line with the corresponding
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OPC concretes. It has also been observed from the experimental results that GPC mixes have

followed similar trend as that of OPC concrete mixes. Like OPC concretes GPCs shown

decrease in the compressive strengths with the increase in AAS/FA ratio (water to cement

ratio in case of OPCs).

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Further, it has been found that, with the decrease in the AAS/FA ratio the compressive

strength increased for both 28 days and 90 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

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

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strengths of GPC mixtures were found to be around 103 to 120% of the 28-day strength. This

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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

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concretes with high activator solution to fly ash ratio. This could be due to the excess solution

present in the system which hinders the polymerisation process in the initial stage (Heah et

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al., 2012). Further, it was observed from the studies that the strengths of GPCs increased
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with age for all the GPC mixes made with various AAS/FA ratios.
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The compressive strength developed in GPC has been found to be more sensitive to

the liquid in the mix design (Albitar et al., 2014). High amount of liquid content than the
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solids in the mixture leads to the decrease in the strength because of the reduced contact
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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
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understand these facts, SEM images of GPC obtained for different solutions to binder ratio
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were shown in Fig. 6. Unreacted fly ash particles were clearly seen in the samples (shown
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with arrow marks). More volume of unreacted fly ash particles can be observed with the

increase 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 the 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
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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

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covered with some unknown films which possibly could have hindered the polymerisation

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process (Arioz and Kockar, 2013).

The overall results showed that excellent compressive strengths can be achieved by

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following the proposed mix design method. All GPC mixes have met their strength

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requirements with respective to the modified ACI strength to water cement ratio curve, for
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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
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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
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efficiently and effectively for regular structural works.

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6. Conclusions
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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.
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As AAS is the costliest ingredient of all, providing flexibility in fixing the AAS content is
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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

corresponding 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

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at varying activator solution to fly ash ratio can be developed. 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.

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Acknowledgment

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The authors are thankful to National Aluminium Company Limited (NALCO), Bhubaneswar

for funding this research work. The financial support is greatly acknowledged.

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Material selection
• Molarity of NaOH
• Na2SiO3 to NaOH ratio
Set the parameters • Curing temperature
• Curing time

Fix the AAS content

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Priority - Strength Priority - AAS/FA

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Select AAS/FA Find the strength for
for target strength selected AAS/FA

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Calculate the binder content
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Determination of activator content
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Calculation of water content in AAS

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Determination of total aggregates

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Calculation of fine and

coarse aggregate content
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Determination No use of SP
of SP dosage
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Strength
requiremen
t

Re-design the Final development

mixture of GPC
DOESN’
SATISFY
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Fig. 1.SATISFY
Flow chart for proposed mix design methodology
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ACI Strength to water cement ratio

relationship of normal concrete
28 day Compressive Strength (MPa)

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40

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20

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0
0.3 0.4 0.5 0.6 0.7 0.8 0.9

w/c ratio
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Fig. 2. Strength versus water to cement ratio curve

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Fig. 3. Mixing and curing of GPC

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Grading curve used for GPC
Standard DIN 'A' grading curve
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Aggregate percentage fraction used
20 mm - 28%
12.5 mm - 32%
60 6.3 mm - 20%
% passing

Fine - 20%

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40

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0.1 1 10
Particle size (log scale) (mm)
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Fig. 4. Combined aggregate grading curve
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60
28 day compressive strength (MPa)

R2 = 0.934
50 28 day compressive strength = 20.352 (AAS/FA) -1.119

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40

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30

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Normal concrete
20 (ACI relationship)
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GPC relationship

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0.3 0.4 0.5 0.6 0.7 0.8 0.9

w/c (or) AAS/FA

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Fig. 5. Comparison of 28 day strengths

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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

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Table 1
Maximum water content per cubic metre of concrete (IS 10262: 2009)

Nominal Maximum water

maximum size of content
aggregate (mm) (kg/m3)
10 208

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20 186
40 165

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Table 2
Mix proportion used in the study

Mix AAS Fly NaOH Na2SiO3 Aggregates (kg/m3) Water SP

/FA Ash /Geopoly

20 12.5 6.3 Fine kg/m3
Kg/m3 Kg/m3 Kg/m3 mer Solid
mm mm mm Aggregate

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1 0.4 500 80 120 465 538 318 320 0.21 6

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2 0.5 400 80 120 500 578 341 344 0.26 4

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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 -

5 0.8 250 80 120

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552 638 377 380 0.37 -
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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

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Table 4
Properties of GPC

AAS/FA Slump 28 day 90 day

(mm) strength strength
(MPa) (MPa)
0.4 35 53.56 55.33

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0.5 60 45.95 47.49
0.6 80 37.12 39.96

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0.7 110 33.41 36.85
0.8 collapse 23.45 28.26

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Research Highlights

Fly ash based GPC s for various AAS/FA ratios can be developed.

Strength vs. w/c (AAS/FA) has been modified to suit GPC mix design.

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GPC with strengths ranging from 23 to 53 MPa can be produced by varying the AAS/FA

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ratio.

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