Thesis Final

Faculty of Engineering
Department of Civil Engineering
THE MIX DESIGN DEVELOPMENT OF GEOPOLYMER
CONCRETE UNDER AMBIENT CURING CONDITIONS

by
Darryl Hole
13110853
October 2009
Civil Engineering Project 461 & 462 Mix Design Development of Geopolymer Concrete
Curtin University of Technology
PROJECT DOCUMENTATION
SHEET

Title: The Mix Design Development of Geopolymer Concrete
Under Ambient Curing Conditions
Author: Darryl Hole

Date: 19th October 2009.

Supervisor: Dr. Natalie Lloyd

ABSTRACT:

Continued increase in the focus and restriction on global carbon dioxide emissions requires the
research for a cleaner alternative to the use of Portland cement. The manufacture of this
product is responsible for the release of millions of tons of carbon dioxide worldwide every
year. Geopolymer concrete consists of 100% fly ash replacement of the ordinary Portland
cement. A binder is formed by a reaction from an alkaline liquid and the aluminium and silicon
present in this fly ash. The present report deals with advancing the mix design research in
geopolymer concrete applications.

The laboratory work carried out for this report was based upon developing geopolymer
concrete mixes that were able to be used in an industry based application, and therefore
having appropriate ambient curing properties. The conditions that would be found on a large
scale concrete project within industry were replicated to form a comparison. Such measures
taken included no specific aggregate preparation (saturated surface dry) or steam room curing.
The aim initially was to consistently produce geopolymer concrete mixes that set quickly and
exhibited a 28 day compressive strength of at least 30 MPa.

Previously successful geopolymer concrete mix designs were used as a basis, with additives
such as silica fume and calcium hydroxide included in anticipation of developing a faster setting
concrete mix with a higher early strength. Seven concrete mixes were produced during the
year with varying mix design properties. Experimental results were based on compressive
strength primarily, with mixes being tested at 7, 14, 21 and 28 days of age in majority of
situations. Tensile strengths were also tested for the first four mixes produced.

Indexing Terms:
Geopolymer, concrete, ambient curing conditions, mix design.
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ACKNOWLEDGEMENTS

I would first of like to particularly thank both my project supervisor Dr. Natalie Lloyd,
and Professor Arie van Riessen from the Curtin University Centre for Materials
Research, for their assistance and direction throughout the year. Further to this, the
assistance of Dr. Dan Churach from the Centre for Sustainable Resource Processing and
Evan Jamieson of Alcoa is acknowledged.

The majority of experimental work for this research was carried out in the Civil
Engineering laboratories at Curtin University, Western Australia. For this I thank the
technical staff including Mr. John Murray, Mr. Mike Ellis, Mr. Ashley Hughes and Mr.
Mike Appleton. I would also like to thank Ms. Monita Olivia for the support and
guidance throughout the year. The progress of this research would have been delayed
significantly without the assistance of these individuals.

The assistance in this research from the Chemical Engineering laboratory at Curtin
University is also acknowledged. Thank you to Ms . Karen Hayes and Ms. Ann Carroll
for their support and assistance throughout the year. Further to this, I would also like
to acknowledge the assistance provided from post‐graduate students from the Curtin
Centre of Materials Research, in particular Ms. Emily Carter, Ms. Melissa Lee and Mr.
Ross Williams.

A final thank you goes to all my friends from the Curtin University Class of Civil
Engineering 2009.

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CONTENTS PAGE

PROJECT DOCUMENTATION SHEET ......................................................................................... i
ACKNOWLEDGEMENTS ........................................................................................................... ii
CONTENTS PAGE .................................................................................................................... iii
LIST OF FIGURES ...................................................................................................................... v
LIST OF TABLES ....................................................................................................................... vi
1. INTRODUCTION .............................................................................................................. 1
1.1 Background ........................................................................................................ 1
1.2 Geopolymer Concrete ........................................................................................ 2
1.3 Research Aims .................................................................................................... 3
1.4 About this Report ............................................................................................... 4
2. LITERATURE REVIEW ...................................................................................................... 5
2.1 Ordinary Portland Cement and the Environment .............................................. 5
2.2 Alternatives to Portland Cement in Concrete .................................................... 7
2.3 Fly Ash based Concretes .................................................................................... 9
2.4 Geopolymer Concrete ...................................................................................... 11
2.5 Mix Proportioning of Geopolymer Concrete ................................................... 14
2.6 Curing of Geopolymer Concrete ...................................................................... 15
2.7 Aiding the Early Strength of Concrete ............................................................. 17
3. EXPERIMENTAL PROCEDURE ........................................................................................ 20
3.1 Introduction ..................................................................................................... 20
3.2 Safety ................................................................................................................ 21
3.3 Materials .......................................................................................................... 22
3.3.1 Fly Ash ............................................................................................................. 22
3.3.2 Sodium Hydroxide ........................................................................................... 22
3.3.3 Sodium Silicate ................................................................................................ 23
3.3.4 Calcium Hydroxide .......................................................................................... 23
3.3.5 Silica Fume ....................................................................................................... 23
3.3.7 Alkaline Liquid ................................................................................................. 24
3.3.8 Aggregate ........................................................................................................ 24
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3.4 Preliminary Laboratory Work ........................................................................... 26
3.4.1 Mixing Procedure ............................................................................................ 27
3.4.2 Mixture Proportions ........................................................................................ 29
3.4.3 Curing of Geopolymer Concrete ..................................................................... 33
3.5 Testing of Concrete Specimens ........................................................................ 34
4. EXPERIMENTAL RESULTS AND DISCUSSION ................................................................. 35
4.1 Introduction ..................................................................................................... 35
4.2 Experimental Results Overview ....................................................................... 35
4.3 Compressive Strength and Observations of Geopolymer Concrete Mixes ..... 40
4.3.1 Initial Geopolymer Concrete Reference Mix ................................................... 40
4.3.2 The Use of Silica Fume to Aid Ambient Curing ............................................... 43
4.3.4 The Effect of Free Water Content on the Strength of Geopolymer Concrete . 48
4.3.3 The Use of Calcium Hydroxide to Aid Ambient Curing ................................... 53
4.4 Indirect Tensile Strength of Geopolymer Concrete ......................................... 63
5. SUMMARY AND CONCLUSIONS ................................................................................... 68
5.1 Introduction ..................................................................................................... 68
5.2 Production of Geopolymer Concrete ............................................................... 68
5.2.1 Pre‐production Issues ..................................................................................... 68
5.3 Results and Observations ................................................................................. 69
5.3.1 The Use of Silica Fume to Aid Ambient Curing ............................................... 69
5.3.2 The Effect of Free Water Content on Geopolymer Concrete .......................... 69
5.3.3 The Use of Calcium Hydroxide to Aid Ambient Curing .................................... 70
5.3.4 Other Observations During Research ............................................................. 70
6. RECOMMENDATIONS ................................................................................................... 72
REFERENCES ......................................................................................................................... 75
APPENDIX A .......................................................................................................................... 79
APPENDIX B .......................................................................................................................... 81
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LIST OF FIGURES

Figure 2.1: Compressive Strength of 30% Fly Ash Substituted Concrete ....................... 18
Figure 3.1: Grading Curve of Combined Aggregates ....................................................... 25
Figure 3.2: Pan Mixer Used for Production of Concrete ................................................. 29
Figure 3.3: Setting of Wet Geopolymer Concrete........................................................... 29
Figure 3.4: Ambient Curing of Geopolymer Concrete .................................................... 33
Figure 3.5: Rough Surface of Cured Geopolymer Cylinder ............................................. 34
Figure 4.1: Compressive Strength of all Carried Out Mixes ............................................ 38
Figure 4.2: Indirect Tensile Strength of Mixes One to Four ............................................ 39
Figure 4.3: Compressive Strength of Mix One ................................................................ 41
Figure 4.4: Efflorescence Formed on the Outside of Cylinders ‐ Mix One at 14 days .... 42
Figure 4.5: Efflorescence on the Outside of Cylinders ‐ Mix One at 28 days .................. 43
Figure 4.6: Expansion of Mix Two (right) Relative to Mix One (left). ............................. 45
Figure 4.7: Expansion of Mix Two Cylinders ................................................................... 45
Figure 4.8: Compressive Strength for Mixes One and Two ............................................ 46
Figure 4.9: Excess Water in Geopolymer Concrete ........................................................ 51
Figure 4.10: Compressive Strength of Mixes One and Four ........................................... 52
Figure 4.11: Compressive Strength of Mixes Three and Four ........................................ 55
Figure 4.12 : Rapid Setting Effects and Efflorescence on Mix Three Cylinders .............. 56
Figure 4.13: Cross Section of Small Cylinder ‐ Mix Three ............................................... 56
Figure 4.14: Mix Six at Two Hours after Pouring ............................................................ 59
Figure 4.15: Mixes Seven (Left) and Six (Right) at One Hour after Pouring .................... 60
Figure 4.16: Compressive Strength of Mixes Five, Six and Seven (MPa) ........................ 61
Figure 4.17: Efflorescence Beginning to Form after De‐moulding ‐ Mix Five ................. 63
Figure 4.18: Indirect Tensile Strength of Mixes One to Four .......................................... 65

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LIST OF TABLES

Table 3.1: Grading of Combined Aggregates .................................................................. 26
Table 3.2: Free Water Content of Mixes One and Two .................................................. 31
Table 3.3: Mix Design Summary of Carried Out Research .............................................. 32
Table 4.1: Mix Design One .............................................................................................. 40
Table 4.2: Compressive Strength of Mix One (MPa) ....................................................... 41
Table 4.3: Mix Designs One and Two .............................................................................. 43
Table 4.4: Compressive Strength of Mix Two (MPa) ...................................................... 46
Table 4.5: Mix Design Four .............................................................................................. 48
Table 4.6: Free Water Content of Mix One ..................................................................... 49
Table 4.7: Free Water Content of Mix Four .................................................................... 50
Table 4.8: Compressive Strength of Mixes One and Four (MPa) .................................... 52
Table 4.9: Mix Design Three ............................................................................................ 53
Table 4.10: Compressive Strength of Mix Three ............................................................. 55
Table 4.11: Mix Designs Five, Six and Seven ................................................................... 58
Table 4.12: Compressive Strength of Mixes Five, Six and Seven (MPa) ......................... 62
Table 4.13: Indirect Tensile Strength of Mixes One to Four ........................................... 65
Table 4.14: Relationship Between Compressive and Tensile Strength .......................... 66

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1. INTRODUCTION

1.1 Background

Concrete is the most widely used structural material in the world, and therefore the
production of it and its constituents are greatly relied upon in industry. The
manufacture of ordinary Portland cement (OPC), the primary binder in a conventional
concrete mix however, is well known for its environmental impacts. Approximately
1.35 million tons of greenhouse gases are emitted through the manufacture of OPC
each year and therefore raises the concern for a cleaner alternative to be developed
(Malhotra 2002).

Continued increase in the focus and restriction on global carbon dioxide emissions
requires the research for a cleaner alternative to the use of Portland cement. Concrete
made using a binder that does not present such environmental issues has been
investigated in the past using fly ash and an alkaline solution. The method of
substituting fly ash for portions of cement in a concrete mix has been established and
is well documented (Huntzinger and Eatmon 2009). However, the use of 100% fly ash
made concrete is limited in industrial applications, partly due to the cost of fly ash and,
in contrast, the availability and convenience of cement. Research fields though are well
interested in the production of concretes with 100% fly ash because of the
sustainability of using this industrial waste product for a construction material.

This report investigates the effects of altering the mix design and properties of
geopolymer concrete. Additives such as silica fume and calcium hydroxide have been
used in anticipation of aiding the ambient temperature curing properties of the
concrete. Further to this, properties of the concrete such as the effect the free water
content has on the final strength have also been investigated. This research deals
exclusively with the ambient curing of geopolymer concrete. This is to simulate site
conditions that a concrete structure may be exposed to, and therefore investigate the
feasibility of in‐situ cast geopolymer concrete.
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1.2 Geopolymer Concrete

The investigation into the use of fly ash‐based geopolymer concretes has increased
since 2000 due to the environmentally sustainable option of using an industrial waste
to form a useful material. Research and industry groups are excited about the prospect
of a concrete made from industrial by‐products that would therefore negate the need
for waste disposal of these materials.

The development of geopolymer concrete mix design has been carried out previously
at Curtin University, Western Australia. Hardjito and Rangan (2005) investigated the
effects of aspects such as alkaline parameters, water content and curing conditions in
“Development and Properties of Low‐Calcium Fly Ash‐Based Geopolymer Concrete”.
Further to this, the production and testing of low scale beams has also been carried
out (Hardjito and Rangan, 2005). The physical properties of geopolymer concrete such
as creep, drying shrinkage and sulfate and acid resistance were also researched at
Curtin (Wallah and Rangan, 2006).

The Centre of Materials Research at Curtin has investigated the use of including
chemical additives to geopolymer pastes in order to increase the early strength under
ambient curing conditions. This paste is essentially an aggregate‐less concrete that is
made in much smaller quantities than the research for this current report. The mix
design properties of geopolymer concrete were investigated by scaling up the
production of geopolymer paste in the form of quantity and by adding aggregate to
the product.

The concrete produced consisted of 77% by mass of aggregate, which is bound by a
geopolymer paste formed by the reaction of the silicon and aluminium within the fly
ash and the alkaline liquid made up of sodium hydroxide and sodium silicate solutions.
Specimens produced were cured only under ambient conditions within the Civil
Engineering laboratory at Curtin University.

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1.3 Research Aims

The present study aims to carry out a scaling up exercise of past work with geopolymer
pastes and mortars that was undertaken by the Materials Research Centre at Curtin
University, and therefore furthering the mix design knowledge of geopolymer concrete
applications. This exercise focuses on progressing towards the production of a
geopolymer concrete with additives included in the mix designs to develop a quicker
setting concrete mix with a higher early strength. It must be noted however, that the
mixing procedure differs greatly between the paste and concrete, as the handling time
and the quantity of material produced is much greater in the production of
geopolymer concrete.

The practical research for this report differs to many previous fly ash based concrete
reports, as the fly ash based concrete is mixed using zero ordinary Portland cement.
Although the production of fly ash does produce large amounts of carbon dioxide
through the burning of coal, the use of it in concrete is seen as a sustainable option
that negates the need for disposal of this waste.

The aim initially was on achieving appropriate mix designs and a mixing procedure that
would consistently provide a 28 day compressive strength of at least 30 MPa.

A conventionally made geopolymer mix utilizing just sodium silicate and sodium
hydroxide with no mix additives was made initially to act as a reference mix. All
subsequent mixes produced were based primarily on this reference mix with materials
either substituted in for fly ash or just as an additive. The mix designs are judged upon
their compressive and tensile strengths accordingly.

The main aims of the laboratory research for this thesis included:
- To familiarize with the making of fly ash based geopolymer concrete.
- To develop an understanding of an appropriate mix procedure in the
production of fly ash based geopolymer concrete.
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- To develop an understanding of appropriate mix proportioning in the
- To observe the strength development of fly ash based geopolymer concrete
under ambient curing conditions.

1.4 About this Report

This report is structured as follows; Chapter 2 presents a brief review of selected
literature related to the environmental tribulations of ordinary Portland cement, the
alternatives to mixing concrete utilizing OPC, and the previous research conducted in
the use of fly ash‐based geopolymer concrete. The general background of geopolymer
concrete production is investigated, along with mix proportioning, mixing procedures
and curing properties.

Chapter 3 describes the experimental process in conducting the research for this
report. Attention is paid to the materials used, mix designs, mixing procedures, curing
conditions and the method of testing the geopolymer concrete specimens produced.

Chapter 4 presents and discusses the results of the research, drawing a comparison
between the final strength and strength development of geopolymer concrete with
varying mix designs cured under site conditions. Any observations noted during the
experimental research being carried out are also stated, with explanations and
justifications to clarify any unknowns.

The present report’s summary and conclusions are included in Chapter 5. This section
is based upon all results and observations discovered in the research throughout the
year.

Further to this, a list of recommendations is given in Chapter 6, detailing suggested
steps in furthering the research in the mix design development of geopolymer
concrete. Concluding this report is a list of references and all relevant appendices.
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2. LITERATURE REVIEW

Chapter 2 presents a background into the environmental impact of the manufacture of
ordinary Portland cement (OPC) and other suggested alternatives to the use of
cement. Research has been undertaken into the previous use of geopolymer concrete,
and the mechanical properties resulting from mix design properties and different
methods of curing.

Research was also conducted into the sustainable qualities of the use of production by‐
products in the manufacture of geopolymer concrete.

2.1 Ordinary Portland Cement and the Environment

Disregarding water, concrete is the most widely used material in the world.
Unfortunately, the manufacture of the integral constituent, ordinary Portland cement
(OPC), proves to be unsustainable with regards to it’s the environmental impact due to
the emissions of carbon dioxide (CO2) and large requirement of energy in the
production procedure. However, due to the high demand for structural materials, the
requirement for cement and concrete will be substantial until an equally effective and
economic alternative is available, and therefore deeming it necessary to either
overlook the environmental impact of standard concrete production, which is highly
unlikely, or develop alternatives that will decrease these effects.

Concrete International recognizes the situation at hand, and the article titled
“Sustainable Development and Concrete Technology” quotes the current issues. ‘The
contribution of ordinary Portland cement production worldwide to greenhouse gas
emissions is estimated to be approximately 1.35 billion tons annually or approximately
7% of the total greenhouse gas emissions to the earth’s atmosphere (Malhotra 2002)’.

The reason large amounts of CO2 are released during the manufacturing of cement is
due in part to the immense heat that is required. The kiln used is heated to
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temperatures of up to 1400°C, and therefore energy requirements to yield this
temperature account for approximately half of the released CO2 in the production of
cement, the second half is released during the calcination process in which calcium
carbonate is reduced to calcium oxide (Hendriks et al. 2003).

The production of cement alone accounts for approximately 5% of the worlds carbon
dioxide emissions. According to the International Energy Agency, approximately 0.81
kilograms of CO2 is generated per kilogram of cement produced annually throughout
the world. The production of cement also produces millions of tons of Cement Kiln
Dust (CKD) which is harmful to the respiratory system (Hendriks et al. 2003).

Due to the increasingly popular requirements for sustainable development within
industry, research into methods of reducing greenhouse gas (GHG) emissions while
maintaining the structural convenience of concrete has been carried out.

The US Concrete Industry has addressed the current GHG emissions incorporated with
the production of concrete in “Vision 2030: A Vision for the US Concrete Industry.” In
this, focus is put on making concrete an environmentally friendly construction material
whilst maintaining its status as the mostly widely used material in industry (Mehta
2001). In recent times, researchers have attempted to produce concrete as an
environmentally friendly product by replacing amounts of ordinary Portland cement
from the mix with industrial by‐products such as fly ash and blast furnace slag.

Global warming continues to be a current concern within the public awareness, and
what effects it will have on the human population in day to day life in the future. The
continuing release of GHG through the burning of fossil fuels and land use change
further increases the risk on earth of a rise in average surface temperatures and the
flow on effects that it will have on sea levels.

Huntzinger and Eatmon (2009) uses life‐cycle analysis (LCA) to evaluate the
environmental impacts and therefore the ‘global warming factor’ of the manufacture
of Portland cement and three other technologies. The three alternatives discussed
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include, “blended cement (natural pozzolans), cement where 100% of the CKD is
recycled into the kiln process, and Portland cement produced where CKD is used to
sequester a portion of the process related to CO2 emissions.”
It was discovered that the most environmentally solution of the three was the blended
cement. Substituting natural pozzolans for OPC will effectively reduce the ‘global
warming factor’ of the product proportional to the amount replaced. In reality though,
it will be seen that in industry, because of the consistent high demand of cement, most
kilns are operating at above their effective capacity. This therefore means that using
‘blended cement’ in industrial applications would not be likely to reduce the net
emissions of carbon dioxide (Huntzinger and Eatmon 2009).

As can be gathered through this review, most of the previous research available looks
at the current situation of cement production and the damage it is causing to the
atmosphere. The next logical step into this investigation is to either prevent this
damage or offer alternatives to concrete using ordinary Portland cement.

It is in the opinion of many, that the use of ordinary Portland cement in concrete is not
going to slow down, despite the ongoing research into alternative binders. It would
therefore be a sustainable decision to investigate further into the mix design of
concrete whilst minimizing the volumes of OPC being used. It would be seen that if the
use of OPC is going to remain strong over the coming decade, keeping its use to a
minimum whilst retaining both durable and workable concrete would provide great
benefit to the GHG emissions.

2.2 Alternatives to Portland Cement in Concrete

As the growth in the world of infrastructure continues, the demand for concrete that is
usable in an industrial application will be high for the foreseeable future. Concrete
using binders other than ordinary Portland cement that leave a smaller carbon
footprint, are therefore heavily investigated within the cement and concrete industry.
The use of these concretes within an industrial application is limited however, and it
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would be fair to say that concrete made without cement has not made a significant
impact into the construction industry yet.

The research into environmentally sustainable concretes is however not limited to
replacing the OPC. Suggestions have been put forward into forming ‘blended cement’
where products such as pozzolans are added to OPC in order to reduce the
environmental effect of the concrete. Concrete that has had OPC replacement
commonly consists of industrial by‐products such as coal fly ash or ground blast
furnace slag (GBFS).

It has been suggested (Damtoft et al. 2008) that the cement and concrete industry is
working positively in the hope of achieving sustainable solutions in environmentally
friendly concrete. He suggests that using hydraulic binders, those which are based on
Portland cement, have an incredible impact on the environment and sustainable
development due to being easily the most widely used construction material
worldwide.
Damtoft et al. also discussed in which ways the industry is acting in order to provide
sustainable development within the field of reducing the environmental impact of
concrete production.
The techniques discussed are as listed below:
- The addition of extra materials to the list of approved supplementary
cementious materials (SCM’s) within current standards.
- Allowing more complex composite cements within current cement standards.
Greater attention to be paid to blending properties.
- Development of methodology for the design of optimal performance for the
use of blended cements.
Damtoft et al. (2008) clearly supports the use and further development of blended
cements in industry, which directly reduces the CO2 emissions to the environment
through replacing volumes of OPC.

The current amount of research into the use of fly ash as a hydraulic binder is far from
limited. The use of coal fly ash in concrete has been investigated for years with very
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positive results for its use in industry. Unfortunately, apart from this research and a
small amount of testing using blast furnace slag, there is little information regarding
the use of other industrial wastes to substitute of ordinary Portland cement in
concretes. The development of a concrete mixture using a new OPC substitute would
greatly progress the process of producing an environmentally friendly concrete. This
coincides with Damtoft’s discussion in which additional materials should be
investigated into their effectiveness of working as a supplementary cementious
material.

2.3 Fly Ash based Concretes

The production of concrete that incorporates the complete replacement of OPC with
industrial by‐products such as coal fly ash has been developed, yet it is far from fully
established. The use of waste products promises to be a sustainable option in any case,
as it negates the need for disposal of these materials, which can become both costly
and of an environmental concern.

Fly ash is a residue that is formed during the combustion of coal. In the past fly ash was
released to the atmosphere during production, but in recent times as research
presents that this previously useless by‐product can be used for other applications, the
capture of it has been instigated. Fly ash’s main constituents are amounts of silicon
dioxide (SiO2), aluminium oxide (Al2O3) and iron oxide (Fe2O3). Fly ash that is destined
for experimental use can be examined in more depth in order to determine its
chemical composition. X‐ray Fluorescence (XRF) analysis is used to determine the
proportions of materials present within the fly ash.

The use of fly ash for concrete production is a popular option in theory, as it is
available abundantly worldwide. The use of 100% fly ash based concrete however, is
limited to date in structural uses. The Ash Development Association of Australia
(ADAA) states that in 2007, Australia alone produced 14.5 million tons of fly ash, and
that only 1.50 million tons (11%) was used in high valued applications such as
cementious or concrete products (Coal Ash Matters 2009).
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Though the practical use of 100% fly ash based in concrete is limited in structural
applications, frequent laboratory work has been conducted into the investigation of
mechanical properties of fly ash based concrete. A recent study at Montana State
University, USA, discussed the method of preparation of fly ash based concrete. It
should be noted that in their experiments, class F fly ash is utilized, in which the
chemical reaction occurring is the hydration of water with the calcium in the fly ash
(Cross, Stephens and Vollmer 2005).

The major hurdle into the use of fly ash based concrete that was noted was the rapid
rate of chemical reaction that occurs once water is added to the mix. It was discovered
that the use of a retarder in these trials were essential, and that in the case that there
was no retardation, hydration would occur immediately and that the concrete would
‘flash set’ in a matter of minutes. It was recommended to the researchers to attempt
the use of borax to delay any setting of the mix, as has been discovered effective with
OPC concretes. It then became an aim of the trials to gain an understanding of under
which conditions the borax needs to be present to extend the placement time before
setting (Cross, Stephens and Vollmer 2005).

It was discovered that the effectiveness of borax was not determined equivalently to
that in OPC based concretes. Rather than a simple relationship connecting the amount
of borax required to the amount of cement used, it was determined that the
effectiveness of the admixture was dependant on its physical properties and the rate
at which it is added to the mix. When the relationships used for OPC based concretes
were attempted to correspond to fly ash based concrete, it was found that the
predicted setting times were largely inaccurate (Cross, Stephens and Vollmer 2005).

The development of fly ash based concrete has a promising future. Laboratory
research carried out worldwide are consistently yielding compressive strengths equal
to or greater than equivalent mix designs utilizing Portland cement. In the above
mentioned report, Cross and Stephens also discovered that fly ash based concrete
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gained strength at a rate equal to or faster than OPC concretes of similar mixes (Cross,
Stephens and Vollmer 2005).
One a physical level, it is thought that the rounded shape of the fly ash particles
maintain the workability of the concrete prior to setting. Fly ash particles are also
smaller in size than that of OPC and therefore produce and more compacted a denser
concrete set.

It should be recognised that the next step in the development of fly ash based
concrete would be research into its durability as a structural material. To date,
concretes with 100% fly ash have been limited to use on low strength applications.
Before this material is to be introduced as a structurally safe and durable material
though, development of mixes, prediction and control of strength, workability and set
times must be obtained. The use of 100% fly ash concrete in these environments
would require the knowledge that it develops soundly under site conditions, such as
curing under ambient temperatures.

2.4 Geopolymer Concrete

Davidovits first proposed that concrete could be made with a hydraulic binder, where
in which the silicon and aluminium from the inclusive fly ash would react with an
alkaline liquid. The reaction that occurs, polymerization, is significantly faster due to
the alkaline conditions. The resultant three dimensional structures consisting of Si‐O‐
Al‐O bonds is a polymeric chain (Davidovits 1999).

The most conventional method of producing geopolymer concrete is the incorporation
of a reaction between the fly ash and an alkaline solution formed from a metal
hydroxide and silicate that forms an alkaline liquid. It is not uncommon for the
constituents of the geopolymer alkaline solution to be sodium hydroxide (NaOH) and
sodium silicate (Na2SiO3). It is common practice in the mix design of geopolymer
concrete, that aggregates occupy anywhere from 70 – 80% in volume by mass.

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Johnson (2008) states that, “Geopolymer consists of silicon and aluminium atoms
bonded via oxygen into a polymer network. Geopolymers are prepared by dissolution
and poly‐condensation reactions between alumino‐silicate binder and an alkaline
silicate solution such as a mixture of an alkali metal silicate and metal hydroxide.”
Again, in the research carried out by Johnson it was noted how quickly the chemical
reactions take place with the addition of the alkaline solution to the fly ash in the
mixing process, therefore limiting the able handling time before setting begins to
occur. Therefore, an aim of the research became that of determining a mixing
procedure that would enable sufficient handling time whilst maintaining a concrete of
workable consistency and could be used in industrial applications. It was discovered
that if a preliminary mixture of the total aggregate volume and the metal hydroxide
solution were formed first, and then the fly ash added, no reaction would take place
until the metal silicate solution was added to the mix. This process of mixing generally
was found to extend handling time up to 45 minutes consistently, and therefore
provide a more suitable application for use on site (Johnson 2007).

Hardjito and Rangan (2005) concluded that it was favourable to mix the sodium
hydroxide and sodium silicate solution at least one day prior to adding it to the dry
materials. This was carried out under recommendation from Davidovits, who observed
that when this was carried out, bleeding and segregation of the concrete no longer
occurred. This combination was then added to the dry mixture.

This is in contrast to advice given to the author of this report by Curtin post graduate
student M. Olivia (personal communication, 25 May, 2009). She advised that the
mixing of sodium hydroxide and sodium silicate solution should occur on the day of
mixing the concrete, otherwise the solution may solidify and the production of
concrete will be extremely difficult. She stressed that research has shown experiences
of the alkaline solution crystallizing before it is to be added to the dry materials,
therefore deeming the pour to be a failure. Situations had also occurred in which the
concrete mix had hardened to a point that it is unable to be poured whilst still in the
mixer.

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Sofi et al. (2007) had similar findings to Johnson (2007) in the research paper entitled
“Engineering Properties of Inorganic Polymer Concretes (IPCs).” In it, he praised the
use of concrete utilizing materials other than OPC in terms of their mechanical
properties. He suggests that inorganic polymer concretes comprising of materials such
as fly ash, can exhibit superior mechanical properties to ordinary Portland cement
concretes. This is heavily dependent though on the chemical composition of the fly ash
used.
The hurdle though, still stands at managing the quick setting nature of geopolymer
concrete, and maintaining the concrete’s ultimate characteristics such as strength and
durability is a prime concern when introducing mixture additions in order to retard the
rapid setting. The fast setting characteristic of IPC, Sofi writes, can be taken as an
advantage or disadvantage. Though the setting of IPC’s can occur rapidly, and the
polymerization reaction occurs straight away, it continues over a length of time which
extends beyond seven days. This contributes to the strength gaining characteristic of
geopolymer which has a distinct behaviour in comparison to OPC based concretes. It
was found within the IPC mixes that between 7 and 28 days, a development of
compressive strength occurred of up to 15 MPa (Sofi et al. 2007).

The use of Geopolymer, to date has only been limited to low strength applications.
This seems to remain the case, when in fact a lot of researchers praise the
characteristics of the product. Johnson (2007) writes in the aforementioned report
that the heat, fire and acid resistance of geopolymer concrete will be greater than that
of Portland cement based concrete. Johnson used the geopolymer’s fast setting
characteristic as an advantage, as he proposed that it be used in the production of
concrete pipes and poles. Such manufacturing requires the use of concrete with zero
slump, and processes that involve centrifugal stages, roller suspension and vertical
casting. It was discovered that by manipulating the mix design, and therefore
producing ‘no slump’ concrete, it was possible to utilize geopolymer concrete in
preparing pipes and other consolidated moulded products.

Another issue that Johnson addressed in the use of geopolymer concrete was the well
known rapid strength gain. He stresses that the time between placement and then
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setting, and therefore losing any plasticity, must be long enough to incorporate any
required transport of the product. This becomes important because if the concrete is
at its hardened state during transport, cracking is likely to occur and therefore a
reduction in the final strength will be experienced. To overcome the associated
problems of rapid strength gain will require control of the setting times of the
concrete, or reverting back to casting products on site or in‐situ, therefore making it
unlikely to have the availability of steam rooms or kilns available for the particular
application.

2.5 Mix Proportioning of Geopolymer Concrete

The aim of the research conducted for this report was to further the mix design of
geopolymer concrete by improving its ambient curing properties. Therefore, the mix
proportioning carried out for this research was in the form of using additives to the
geopolymer concrete mix, rather than re‐establishing standard mixes again. This
meant that initial mix designs were based largely upon previously successful
geopolymer concrete mixes that had already yielded substantial results.

It was found by Hardjito and Rangan (2005) that consistent results were gained upon
keeping the alkaline solution at a sodium silicate‐to‐sodium hydroxide ratio of 2.5. This
ratio was favoured over a lesser one because of the reliable results that it yielded, and
because the sodium silicate solution is considerably cheaper than the sodium
hydroxide pellets. A general proportion of alkaline solution‐to‐fly ash was settled upon
at approximately 0.35. Upon investigation of the affects of the concentration of the
sodium hydroxide solution, it was found that in mix designs of exact proportions, the
mix with the higher concentration in molarity of the sodium hydroxide solution would
yield a higher compressive strength. This was examined through the use of varying the
molarity of the solution between 8 molars and 14 molars in mix designs of exact
proportions.

Liu reports how geopolymer concrete can be produced by using other industrial wastes
such as bauxite residues. It is noted how past research into the re‐use of these
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products such as bayer liquor has been used to produce materials such as ceramics,
cements, clay bricks and glazes. In the production of unsintered construction and
building products, Liu suggested that the optimal proportions of raw materials show
following:
Bauxite Residue : 25 – 40%
Fly Ash : 18 – 28%
Sand : 30 ‐35%
Lime : 8 – 10%
Gypsum : 1 – 3%
Portland Cement : 1%
This composition has been used to produce building materials that has reached the 1st
grade of Chinese standards for a brick (Liu et al. 2009).

2.6 Curing of Geopolymer Concrete

The present report deals with the ambient curing of geopolymer concrete, yet
changing the method of curing has previously researched in geopolymer concrete. The
ability of concrete to cure at ambient temperatures becomes useful in industrial
applications when concrete is cast in‐situ or on site, as the availability of a kiln,
especially on larger scale projects, is unlikely.

The conditions under which geopolymer concrete is cured directly relates to the
durability and strength of the mix, as displayed by Hardjito et al. (2004). His results
found that the curing of concrete at higher temperatures, up to 60°C, yielded a higher
compressive strength than at a lower temperature, yet any increase in curing
temperature over this threshold made no substantial difference to its strength. A
proportional relationship was discovered between the length of curing time and
compressive strength. The rate of setting of geopolymer concrete is well documented,
yet it is likely that these cases were resultant upon short curing times. Hardjito et al.
discovered the fast rate of polymerization only stalled the strength gain when the
concrete was cured for short times, such as 24 hours. This contrasts with the strength
development behaviour of OPC based concretes, which undergo a hydration process
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over a length of time when being steam cured, therefore increasing in strength with
age. This strength development over time can be achieved with geopolymer concrete
when curing time is extended. It was discovered that as the curing time increases in
the range of 6 hours to 96 hours (4 days), the polymerization process is improved and
therefore yields a higher compressive strength. It is noted though, that the strength
increase after 48 hours of steam curing is not significant.

It is recommended that during curing of geopolymer concretes at elevated
temperatures, samples should be wrapped and then sealed, this should be present for
the duration that the samples are being cured at temperatures up to 100°C. This
precaution has been suggested in order to prevent excessive evaporation of the
samples during curing. This would cause a less dense concrete with a weaker
compressive strength. It was also discovered that in wrapping the geopolymer
concrete specimens, the mix did not harden immediately under ambient conditions. At
room temperatures of below 30°C, hardening of the concrete did not occur for at least
24 hours (Hardjito and Rangan 2005).

Whilst interesting to know that it is possible to achieve a time‐dependant, strength‐
development behaviour with geopolymer concrete, in industry, it would not be very
applicable. Rarely would you see concrete cast and then kept under controlled curing
conditions for any more than 24 hours, and if it was cast in situ, all curing would be
under ambient conditions. In a rare situation where formwork turnover is not as
critical in a precast concrete environment, it would be possible to achieve an extended
curing time under controlled conditions.

Wallah and Rangan (2006) reported how the strength development of geopolymer
concrete varied with the conditions under which they were cured. Three batches of
the same mix were produced at varying times in the year; May, July and September
2005, and cured under ambient conditions within the laboratory. The cylinders were
released from their moulds one day after casting. It was discovered that specimens
cured under ambient conditions exhibited significantly lower 7 day compressive
strengths than those cured under elevated temperatures for the first 24 hours.
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It was reported that under ambient curing conditions of geopolymer concrete, the 7th
day compressive strength and subsequent strength gain with respect to age lies
dependent upon the average ambient temperature at the time of curing. As the
ambient temperature at casting increased, as did the 7th day and subsequent
compressive strength’s tested at later dates. The compressive strength of the
geopolymer concrete during July exhibited a 28 day strength of 31 MPa in comparison
to 47 MPa for the mix poured in May. The average temperature experienced within
July 2005 ranged from 8°C to 18°C, and 18°C to 25°C in May (Wallah and Rangan 2006).

2.7 Aiding the Early Strength of Concrete

The reaction between elements in fly ash based concretes is a slow process, and
therefore only contributes to the strength development at later dates of age. This
causes a problem in the utilization of fly ash concrete in ambient cured precast
concrete applications, due to the low early strength and formwork turnover routines.
Previous research in OPC based concretes has indicated that the inclusion of silica
fume and hydrated lime (calcium hydroxide) yields positive results in increasing the
early strength of concrete, as well as having the concrete mix set quicker.

Barbhuiya et al (2009) investigated the use of including silica fume and calcium
hydroxide to concretes with a fly ash substitution of 30% of the ordinary Portland
cement based content. Silica fume was added to the mix at 5% by mass of the cement
content as a final addition when mixing the concrete. Hydrated lime on the other hand
was substituted at a rate of 5% by mass of the total cementious materials. In order to
investigate the early strength development of this concrete specimens were tested at
3, 7 and 28 days after casting. Specimens were cured in curing rooms at constant
temperatures. The first 24 hours were spent at 20°C and then transferred to a moist
curing room at 23°C and kept in water until testing.

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Workability is seen to decrease upon the addition of hydrated lime, however to
improve this, a super plasticiser was added. The addition of silica fume to the mix had
no effect on the workability of a concrete mix.

It was discovered that the addition of both silica fume and calcium hydroxide increased
the early compressive strength of the concrete mixes. Testing at 3 days of age showed
that the strength of both silica fume and hydrated lime mixes were equally higher, (30
MPa) than the standard concrete mix at 24 MPa. The major differences in compressive
strengths were apparent at 28 days with a constant progression from the standard mix
(49 MPa), fly ash inclusive of hydrated lime (53 MPa) and then the concrete mix
incorporating silica fume with a 58 MPa 28 day compressive strength (Figure 2.1).

Figure 2.1: Compressive Strength of 30% Fly Ash Substituted Concrete

The use of calcium based additives into geopolymer pastes was researched by
Temuujin, van Riessen and Williams (2009). Both calcium hydroxide and calcium oxide
were substituted into geopolymer pastes for fly ash in order to accelerate the ambient
curing (on average at 20°C) of the paste, and increase the compressive strength under
these curing conditions. To form a proper comparison between the effects from curing
conditions, specimens were oven cured being subjected to heats of 70°C.

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It was found that the addition of calcium compounds improved the mechanical
properties of geopolymer pastes cured at ambient temperatures, yet reduced the
strength of those cured under elevated temperatures.

The results also showed that the addition of calcium hydroxide (Ca(OH)2) aided the
ambient curing strength more so than calcium oxide (CaO). It is suggested that this is
apparent because the calcium hydroxide is a reactive constituent of the geopolymer
mixes. The use of calcium hydroxide would appear to present incomplete hydration of
the product as it reacts with the alkaline solution in the formation of calcium
hydroxide. Specimens with CaO added presented compressive strengths approximately
20% lower than those with calcium hydroxide.

It is suggested that the lower compressive strength in the pastes that is cured under
elevated temperatures is due to the water evaporation within the mix, exhibited by
lower density and higher porosity. At elevated temperatures, it is also suggested that
the presence of calcium doesn’t allow the formation of three dimensional geopolymer
network due to the fast dissolution of the paste. This therefore results in reduced
mechanical properties of the final product. Under ambient conditions, it was found
that by increasing the percentage of added calcium compound, the compressive
strength increased with it. With a 3% addition of calcium hydroxide the compressive
strength of 29 MPa compared to a geopolymer paste with no calcium additive which
exhibited a strength of 12 MPa. In comparison, geopolymer with a calcium hydroxide
inclusion of 1% and 2% showed strength of 24 MPa and 28 MPa respectively
(Temuujin, van Riessen and Williams 2009).
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3. EXPERIMENTAL PROCEDURE

3.1 Introduction

Chapter 3 presents the details of the research that was carried out in order to
investigate the inclusion of additives in the development of geopolymer concrete mix
design.

Due to the limited research conducted using fly ash‐based geopolymer concrete with
zero OPC, a large part of the experimental work for this report focused on the mix
proportioning and procedure for developing this concrete. The project’s aim included
mix design development that would constantly yield concrete mixes with a consistent
compressive strength of at least 30 MPa.

Due to the lack of previous mix design information using geopolymer concrete, initial
mix design and procedures closely followed regular conditions for the production of
geopolymer concrete using sodium hydroxide (NaOH) and sodium silicate (Na2SiO3) to
form the alkaline solution. A trial and error process was then used for fine tuning the
strength of the mixes, including materials such as silica fume and calcium hydroxide in
anticipation of developing a concrete mix that would cure faster and develop a higher
compressive strength.

Experimental results were based upon compressive and tensile strengths, this is not
unusual because compressive strength has a fundamental importance in the design of
concrete structures. Tests for these parameters were for the majority of the mixes
conducted at 7, 14, 21 and 28 days after casting. This was conducted to observe the
short term strength development in concrete with the primary binder not being
cement.

The current methods of producing and testing of ordinary Portland cement concrete
were followed as closely as possible in the production of this geopolymer concrete.
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This was a key point in the research, as it was important that a relevant comparison

between the two products was formed and therefore investigating whether
geopolymer concrete would be suitable to be produced on site. This included a general
aggregate quantity of 77% by mass within the mix. The aggregate used within the
different mixes originate from the same source throughout the year, in order to
minimize the effect of varying aggregate properties.

3.2 Safety

Prior to any research beginning, an aim for this report was to develop a geopolymer
concrete mix utilizing bayer liquor. This product is an industrial waste that is formed in
the stage of removing bauxite in the refining of alumina. It has previously been used in
the production of geopolymer pastes by the Centre of Materials Research department
at Curtin University. The aim was to carry out a scaling up exercise of this paste by
adding aggregates to the mix and increasing the quantity produced.

In order to gain access to the bayer liquor, numerous precautions needed to be carried
out, due to the caustic nature of the product. The most important of these was the
Edusafe risk analysis and compliance. This took into account what measures needed to
be put in place so that safe handling procedures of this material could be carried out. A
major influence that this programme had on the preparation was the requirement for
a safety shower to be installed in the laboratory. Strict methods of storage and
disposal also had to be planned that comply with the appropriate measures as outlined
on the product’s Material Safety Data Sheet.

Due to the unsafe nature of the product and the relatively tight schedule to put all
safety measures in place, the bayer liquor was not able to be brought to Curtin for use
in concrete. These measures were also carried out for production of the conventional
geopolymer concrete, however the procedure for the bayer was quite a bit more
stringent due to it never having been used in concrete at Curtin University.

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3.3 Materials

3.3.1 Fly Ash

The carried out experimental work utilized low calcium Class F fly ash obtained from
Collie Power Station located south of Perth, Western Australia. Throughout the
research, the fly ash used was from the same delivered batch. The fly ash was obtained
in bulk bags and measured from here into the respective amounts required.

3.3.2 Sodium Hydroxide

A sodium hydroxide solution was utilized in all mixes as a constituent in the alkaline
reactor. The product was obtained from a local supplier in the form of pellets with a
purity of 98%. The solution was prepared by dissolving the pellets into distilled water
at specified concentration in molars, M, for the concrete. In the laboratory research
carried out, the solution was prepared with a concentration of approximately 10 M by
dissolving the sodium hydroxide solids into distilled water.

To produce 1 kg of sodium hydroxide solution, 416.8 grams of pellets was dissolved
into 583.2 grams of distilled water. The solid was added to the water gradually and
stirred for approximately 20 minutes until all solid had dissolved. It was noticed that
upon addition of the solid to water, the solution became hot as the exothermic
reaction of dissolution carried out.

Upon preparation of the first mix produced, the sodium hydroxide solution was
prepared 4 days prior to its addition to sodium silicate, and then production of
concrete. It was discovered that after 4 days of standing, some sodium hydroxide
solids had appeared in the solution after being dissolved completely when initially
combined, this required stirring of approximately half an hour to reduce the solid
content. Subsequent sodium hydroxide solutions made throughout the year were not
prepared to a schedule prior to mixing the concrete. Generally though, dilution of
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sodium hydroxide occurred a few days before concrete production in order to limit the
time spent preparing the chemicals on the concrete mixing day.

3.3.3 Sodium Silicate

The sodium silicate was obtained in 30.5 kilogram pallets from a local chemical
supplier, PQ Australia. The grade of material used is known as PQ‐D with a SiO2/Na2O
ratio of 2.0. The pH of this liquid was 11.9 and was in the form of a heavy syrup.
The weight analysis of this material was as given by the supplier:
Na2O : 14.7%
SiO2 : 29.4%
Water : 55.9%
No dilution was required, after being weighed out it was used in the concrete as
delivered.

3.3.4 Calcium Hydroxide

The calcium hydroxide used in Mix Three is known as HYLIME by Cockburn Cement. It
was an industrial grade powder obtainable from the local hardware store, typically
used in masonry mortars or plastering applications. This product was used in
anticipation of developing a faster curing concrete with a higher early strength.

XRF analysis carried out on the product shows the majority of the composition of
HYLIME to consist of 84% by mass of calcium oxide, 7.2% silicon dioxide and 5.3%
magnesium oxide.

3.3.5 Silica Fume

Silica fume was used in Mix Two as a fly ash replacement in hope that it would aid the
ambient curing properties of the concrete.

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The silica fume used was obtained from local supplier Simcoa, Western Australia. The
product was delivered in bags of 10 kilograms, and was known just as Microsilica or
densified silica fume. This same product is also used in concrete batching plants in
Western Australia, in particular for marine applications. The silica fume is in the form
of extremely fine particles and therefore makes the concrete less impermeable upon
addition.

3.3.7 Alkaline Liquid

The alkaline solutions for all mixes produced during the research were prepared by
combining the sodium hydroxide solution to sodium silicate gradually. This mixture
was then stirred moderately for a few minutes and then sealed in the buckets with lids
until addition to the concrete mix. This process took place immediately prior to
beginning production of the concrete, the ratio of sodium silicate to sodium hydroxide
was kept consistent at 2.5 upon recommendation from Hardjito and Rangan (2005).

3.3.8 Aggregate

The aggregate used was supplied by Cemex to Curtin University, stored outside
uncovered in storage divisions. The aggregate supplied consisted of two components;
coarse aggregate obtained from the Cemex Gosnells Quarry and a fine aggregate that
originated from Baldivis Sand. For the purpose of this research, coarse aggregates
were used with nominal sizes of 7mm, 10mm and 20mm, and fine aggregates in the
form of sand.

The aggregate was measured approximately a week prior to pouring and sealed in
bins. The moisture content of the aggregate was measured at the time of being used in
the concrete, and subsequently used to determine the free water content of the
concrete mix.

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The aggregate proportions were found in accordance with utilizing British Standards BS
882.92 (Neville 2000, 172) grading requirement limits for all‐in aggregate. The grading
curve was constructed in order to satisfy the grading limits with an application sourced
from the University of Patras.

As can be seen the sieve analysis of the utilized aggregate displayed a grading‐gap,
which is displayed on the grading curve below (Figure 3.1). This made proportioning
the aggregate components a more stringent process. Neville (2000) suggests that a
grading curve closer to the bottom limit is comparatively workable, and can therefore
be used in mixes with a low liquid/binder ratio. The results of sieve analysis and
grading combinations of the utilized aggregates can be seen below in Table 3.1.

0.063
0.15
4.75
0.6
19
ISO Sieve
100 100
95
90
80
70
Percentage passing
60
50 50
40
35
30 30.5 30
27.5 30.1
20
10 10
6
5.5
0 0 . 0 1 m m 0 . 1 m m
1
0 0.7 1 m m 1 0 m m 1 0 0 m m
BS Sieve
Particle size (mm)
Figure 3.1: Grading Curve of Combined Aggregates
(Grading Curve 2009)

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Table 3.1: Grading of Combined Aggregates
Aggregates
Sieve Combination BS 882.92
20 mm 10 mm 7 mm Fine
19.00 mm 98.10 100.00 100.00 100.00 99.43 95‐100
9.50 mm 0.19 90.68 100.00 100.00 68.66
4.75 mm 0.14 1.16 44.67 99.94 41.37 35‐55
2.36 mm 0.14 0.71 1.49 99.78 30.46
1.18 mm 0.14 0.69 0.52 99.47 30.12
600 μm 0.14 0.69 0.37 70.98 21.53 10‐35
300 μm 0.13 0.68 0.25 17.81 5.55
150 μm 0.11 0.66 0.11 1.96 0.75 0‐8
Ratio 30 15 25 30

3.4 Preliminary Laboratory Work

The aim of this research was to gain a knowledge and understanding of the effect of
altering mix designs in a geopolymer concrete mix. Due to the lack of experience in any
geopolymer concrete production by the author, it was suggested that to begin with, a
standard geopolymer concrete mix using the established sodium hydroxide and
sodium silicate alkaline solution would be made first to familiarize with the process
and use a reference to other mixes.

The first two mixes were undertaken at the beginning of June, 2009, with the use of
the 70 litre capacity pan mixer (Figure 3.2) to produce approximately 65 litres (156
kilograms) of geopolymer concrete. Samples were placed in test specimens, 100mm x
200mm compression cylinders and 150mm x 300mm tensile cylinders, and cured
under the ambient conditions after pouring.

The preliminary laboratory works focused on the following main objectives:

- To familiarize with the making of fly ash based geopolymer concrete.
- To develop an understanding of an appropriate mix procedure in the
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- To develop an understanding of appropriate mix proportioning in the
- To observe the strength development of fly ash based geopolymer concrete
under ambient curing conditions.

3.4.1 Mixing Procedure

The mixing procedure plays a vital role in the production of geopolymer concrete due
to the unstable nature of some mixes. If constituents are added in the wrong order, it
is possible that the concrete may flash set in the mixer, causing both a failed mix and a
tough clean up. For this reason, a particular order was followed in the concrete mixing
during this research.

Cylinder moulds were first prepared for concrete pouring by coating them with mould
release. For the use of geopolymer concrete, a product by the name of Valsof PE‐40
was used as the mould release, as the usual grease would not work the same as with
cement based concretes.

The alkaline solution consisting of sodium hydroxide and sodium silicate was combined
at the beginning of the day when producing concrete. This came under
recommendation in order to avoid the solution crystallizing over a long stationary
period, an outcome that would deem the concrete mix design to differ if water was
used to dissolve the solid again. The sodium hydroxide solution was added carefully to
the second constituent and mixed thoroughly, before being sealed with lids prior to
mixing time.

The mixing procedure for geopolymer concrete was similar to that of conventional OPC
concrete. All dry aggregates and fly ash were first added to the pan mixer and mixed
for a few minutes to properly combine all sizes. After this dry mixing, the alkaline
solution and any extra water was then added gradually and then mixed for a further
three minutes, or, until an adequately combined mixture was formed.

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At the conclusion of this wet mixing, any mix design additives such as silica fume or
calcium hydroxide were added and again mixed thoroughly for approximately three to
four minutes. This was carried out so that in the event of a rapid setting mix, it would
be obvious that the final added constituent was the contributing factor.

The produced geopolymer concrete differed physically to concrete made with ordinary
Portland cement. Geopolymer concrete is very dark in colour (a dark brown
appearance) and has an extremely ‘sticky’ feel to it. The placement of the concrete
into cylinders therefore took longer than expected due to the difficulty of moving the
concrete after mixing.

Cylinders were filled to approximately half way before being vibrated for a few
minutes or until no bubbles were being formed at the surface. The cylinders were then
filled to the top and vibration started again, each mould being topped up as the
vibration caused the elimination of any air voids. Only a small amount of time on the
vibration table was given to those mixes with a high free water content as it was
discovered that excessive movement of these mixes caused segregation of the
aggregates and the top of the cylinders became more of a paste.

Upon completion of the concrete placement, cylinders were moved from the table to
an area in the labs for setting under ambient conditions, as seen in Figure 3.3 below.

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Figure 3.2: Pan Mixer Used for Production of Concrete

Figure 3.3: Setting of Wet Geopolymer Concrete
3.4.2 Mixture Proportions

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Hardjito and Rangan (2005) have stated that using a higher molarity of sodium
hydroxide solution within the alkaline mix will yield a higher strength concrete. In their
experimental results it was seen that, in otherwise similar mixes, using NaOH with
concentration of 14M as opposed to 8M consistently yielded higher compressive
strengths.

Knowing this, when preparing the sodium hydroxide prior to producing the
geopolymer concrete, solutions of 10M were prepared in anticipation of returning the
highest possible compressive strength in the given situation.

Mix One (poured in June, 2009) was proportioned in accordance to the research by
Hardjito and Rangan (2006), with a 10M sodium hydroxide solution, aggregate content
of 77%, sodium silicate to sodium hydroxide ratio of 2.5, and an alkaline liquid to fly
ash ratio of 0.35.

Water was added to the first mix produced in anticipation of yielding a workable mix
that was easy to place, as the moisture content of the aggregate used was quite low.
This mix was used as a datum for further mix designs, as the amount of water used,
combined with the moisture content of the aggregate, would be used as a reference of
the amount of water in future mixes. It was discovered for Mix One that 1.5 litres of
water was required to be added to gain an adequate workability of the mix. A
summary of this first produced mixes water content is found below in Table 3.2.

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Table 3.2: Free Water Content of Mixes One and Two
MIX ONE
Water Mass of Water
Aggregate
Content (%) Aggregate (kg) Content (kg)
20mm 0.45 36 0.16
10mm 0.69 18 0.12
7mm 1.64 30 0.49
Sand 0.42 36 0.15

Added Water 1.5

Alkaline Solution 1.6

Total Free Water
Content (kg) 4.0
Total Free Water
Content (%) 2.6

f'cm.28 (MPa) 30

Throughout the year, seven geopolymer concrete mix designs were produced in order
to gain a relevant comparison in the effect of altering the concrete mix properties. The
final mix designs, in terms of mass of material included per cubic metre of concrete
produced, are found in Table 3.3 below. A summary of each mix design and its overall
performance is also provided in Appendix A.

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Table 3.3: Mix Design Summary of Carried Out Research
MIX ONE MIX TWO MIX THREE MIX FOUR MIX FIVE MIX SIX MIX SEVEN
Materials kg/m3 kg kg/m3 kg kg/m3 kg kg/m3 kg kg/m3 kg kg/m3 kg kg/m3 kg
20 mm 554 36 554 36 554 36 554 39 554 5.5 554 5.5 554 5.5
10 mm 277 18 277 18 277 18 277 19 277 2.8 277 2.8 277 2.8
7 mm 462 30 462 30 462 30 462 32 462 4.6 462 4.6 462 4.6
Sand 554 36 554 36 554 36 554 39 554 5.5 554 5.5 554 5.5
Fly Ash 408 27 362 24 380 25 408 29 408 4.1 408 4.1 408 4.1
Sodium Silicate 103 6.7 103 6.7 103 6.7 103 7.2 103 1.0 103 1.0 103 1.0
Sodium Hydroxide 41 2.7 41 2.7 41 2.7 41 2.9 41 0.4 41 0.4 41 0.4
Silica Fume - - 46 3.0 - - - - - - - - - -
Calcium Hydroxide - - - - 28 1.8 - - 2.8 0.03 5.5 0.1 17 0.2
Extra Water 23 1.5 23 1.5 - - - - 96 1.0 96 1.0 96 1.0
TOTAL 2423 157.5 2423 157.5 2400 156.0 2400 168.0 2499 25.0 2502 25.0 2513 25.1

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3.4.3 Curing of Geopolymer Concrete

The geopolymer concrete specimens produced for this research were cured under
ambient temperatures. Due to having no exposure to elevated temperatures under
ambient conditions, the cylinders did not have to be wrapped in plastic to prevent
excessive evaporation. Therefore, the specimens were left uncovered in the laboratory
until set.

The first mix made revealed that under ambient conditions; the geopolymer concrete
did not set until 6 days after pouring. Therefore, the cylinders remained in their
moulds for the first week of curing. This also meant that compressive testing was not
carried out at 3 days after pouring as was first anticipated.

The first compression tests were undertaken at 7 days after pouring, and therefore all
cylinder moulds were released at this time. From this time onwards, specimens
remained under the same ambient conditions, only with their full surface area
exposed. The first two mixes were poured at the beginning of June, 2009. The outside
temperature during this month in Perth, Western Australia, varied between 3°C and
26°C (Bureau of Meteorology 2009).

Figure 3.4: Ambient Curing of Geopolymer Concrete
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3.5 Testing of Concrete Specimens

The compressive and tensile strength testing of the concrete cylinders was for majority
of the mixes undertaken at 7, 14, 21 and 28 days after pouring. The testing was
performed using a 300 ton capacity Controls MCC8 hydraulic testing machine in
accordance to AS1012.10 – 2000 and AS1012.9‐2000 for tensile and compressive test
respectively.

Compressive strength was determined using three 100x200 mm concrete cylinders at
all 4 testing days, while the indirect tensile tests we carried out on three 150x300 mm
cylinders at 14 and 28 days after pouring. Due to the top surface condition of the
compressive specimens, sulfur caps were made for the cylinders to ensure that the
compression force is transferred equally across the top of the surface. Figure 3.5
shows the exposed surface of the concrete, with aggregate particles exposed making
an uneven surface, and the sulfur cap used to produce the even surface for testing.

Figure 3.5: Rough Surface of Cured Geopolymer Cylinder
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4. EXPERIMENTAL RESULTS AND

DISCUSSION

4.1 Introduction

Chapter 4 presents the experimental results obtained during the year, and the
discussion regarding the relevance and significance of these findings. The concrete
strengths discussed in this chapter correspond to the mean value of strength from
three test specimens in a series. All significant observations and occurrences are also
noted with the results of the relevant concrete mix.

For individual cylinder data, details and strengths see Appendix B.

In this chapter, the effects on the strength of fly ash based geopolymer concrete within
the mix design and preparation are compared and discussed. The different parameters
considered within this research include:
1. A standard geopolymer concrete reference mix (Mix One).
2. The effect of adding silica fume to aid the ambient curing properties of
geopolymer concrete (Mix Two).
3. The effect of a high free water content on the strength of geopolymer
concrete (Mix Four).
4. The effect of adding calcium hydroxide to aid ambient curing properties of
geopolymer concrete (Mix Three, Mix Five, Mix Six and Mix Seven).

4.2 Experimental Results Overview

The experimental results throughout the research for each mix are used in comparison
to Mix One, a conventional geopolymer concrete mix with no additives used in any
attempt to enhance its performance. The initial aim for these mix designs was to
consistently prepare concrete mixes that would yield a 28 day strength of at least 30
MPa, which is exactly what Mix One came out to be.
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The further mix designs did not yield as positive results as what was initially expected.
The addition of silica fume to the mix created an inordinate amount of silicon in the
concrete which had drastic negative effects on the final strength, exhibiting a 28 day
strength of 12.8 MPa. Mix Two however did set slightly quicker with the addition of
silica fume than Mix One and could therefore in theory be used under low strength
geopolymer concrete applications being set under ambient conditions.

The effect of raising the free water content of the concrete mix yielded the result that
was expected in Mix Four. In fact at the first testing at 7 days, it was predicted that the
concrete had not properly set, given the extremely low strength of 2.5 MPa. This
however was dispelled at the 28 day test with a final strength of only 10.8 MPa. It was
therefore seen that by doubling the water content of the mix, the resulting final
strength of the concrete is in effect one third of the reference Mix One.

Because of the nature of by which the aggregates were stored outside during the
winter months, all further mixes now exhibited extremely wet aggregates leading to a
high free water content. Therefore Mix Four was now used as a reference mix as to
match the free water content of all further mixes and comparing compressive and
tensile strengths of the concrete. As previously explained, aggregates were not
specifically prepared to simulate a large scale concrete production.

Mix Three incorporated the use of calcium hydroxide (hydrated lime) in order to both
quicken the curing time for the concrete and produce a higher final strength. Even with
a moderately low amount of lime used (5% of the geopolymer, replacement of fly ash),
the mix flash‐set in the pan mixer before being completely placed in the moulds. This
mix design would therefore not be applicable in an industry operation where large
quantities of material are produced. The unaffected cylinders were still tested and
showed positive results for a mix with a high free water content with a final strength of
18.2 MPa, comparative to Mix Four’s reference strength of 10.8 MPa.

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To further the investigation into the use of calcium hydroxide in geopolymer concrete,
a further three mixes were prepared with varying quantities of the product. This was
carried out to investigate what composition of hydrated lime caused a geopolymer
concrete mix to set too quickly to place. Mixes Five, Six and Seven were produced with
an addition of 0.5%, 1% and 3% of the geopolymer paste respectively, this time
however the calcium hydroxide was added to the concrete mix without replacement of
the fly ash. Again the mix was produced with high water content in order to produce a
relative comparison with Mix Three and Four.

Despite all three setting noticeably quicker than the standard mix, Mixes Five, Six and
Seven showed no significant increase in strength at 28 days of age. What was even
more unexpected was that Mixes Five and Six were significantly lower than the
reference. Of the three differing amounts of calcium hydroxide used, Mix Six which
contained an addition of 3% of the geopolymer exhibited the highest compressive
strength of 11.0 MPa, just slightly above the 10.8 MPa reference of Mix Four.

The resulting compressive strengths as strength develops over the first 28 days from
pouring can be seen in the below Figure 4.1.

The indirect tensile strengths were also determined for Mixes One to Four. The 28 day
tensile strength for the majority proved proportional to compressive strength results,
with Mixes One and Three ending up the strongest with 2.7 and 2.2 MPa respectively.
It was seen that the relationship between the compressive and indirect tensile
strength was extremely similar to one proposed by Neville (2000) suggesting:
Fct = 0.3 fcm⅔
A relationship determined by Lloyd and Rangan (2009) for geopolymer concrete was
not adhered to primarily due to a contrast in curing conditions. Lloyd and Rangan
developed this relationship using geopolymer concrete specimens cured in the steam
room, where as the laboratory work for this report was based on ambient curing.

The indirect tensile strength of Mixes One to Four is shown below in Figure 4.2.

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Compressive Strength of Geopolymer Concrete (MPa)

35
30
25
Compressive Strength (MPa)
20
Mix One
Mix Two
15
Mix Four
Mix Three
Mix Five
10
Mix Six
Mix Seven
5
0
0 5 10 15 20 25 30
Age After Pouring (Days)

Figure 4.1: Compressive Strength of all Carried Out Mixes
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3
Tensile Strength of Geopolymer Concrete (MPa)
2.5
Tensile Strength (MPa)
1.5 Mix One
Mix Two
Mix Three
Mix Four
1
0.5
0
0 5 10 15 20 25 30
Figure 4.2: Indirect Tensile Strength of Mixes One to Four
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4.3 Compressive Strength and Observations of Geopolymer

Concrete Mixes

4.3.1 Initial Geopolymer Concrete Reference Mix

Table 4.1: Mix Design One
MIX ONE
Materials kg/m3 kg
20 mm 554 36
10 mm 277 18
7 mm 462 30
Sand 554 36
Fly Ash 408 27
Sodium Silicate 103 6.7
Sodium Hydroxide 41 2.7
Silica Fume - -
Calcium Hydroxide - -
Extra Water 23 1.5
TOTAL 2400 157.5

Mix one was prepared in anticipation of it being the ‘reference mix’ by which to
compare other mixes made. This was seen as the standard geopolymer concrete mix
and all further mix designs were based on this with variations in quantities of materials
used and additives included. Mix One was prepared in early June 2009 at the
immediate beginning of the laboratory work conducted for this report.

Mix One exhibited a 28 day strength of exactly 30 MPa, coincidentally the benchmark
strength upon which all further mixes were expected to exceed. The shape of the
strength development curve, as shown in Figure 4.3 also indicates that given extra
curing time under these ambient conditions, a higher strength could be attained. Of
the three mixes made throughout the year which was at regular intervals, Mix One is
the only one that shows a still developing strength curve and promises to provide
worthwhile higher strengths at an age beyond that of 28 days.

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Table 4.2: Compressive Strength of Mix One (MPa)
MIX ONE
Age in Compressive Standard Number of
Days Strength (MPa) Deviation Samples
0 0.0 0.00 -
7 8.6 0.19 3
14 17 0.65 3
21 24 0.30 3
28 30 0.25 3


35
30
25
20
Mix One
Mix Two
15 Mix Four
Mix Three
10
0
0 5 10 15 20 25 30

Figure 4.3: Compressive Strength of Mix One

It was also noticed that an efflorescence precipitate was formed on the outside of the
cylinders on Mix One. The efflorescence was in the form of a white crystal, and was
apparent at 14 days after pouring. The amount of efflorescence changed too as the
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age of the concrete lengthened, and by 28 days the specimens had a substantial
coating of material on the outside. Temuujin, van Riessen and Williams (2009)
discovered similar findings on ambient cured geopolymer paste samples when using
additives to aid mechanical properties of the paste under ambient curing conditions. It
was led to believe that the efflorescence formed was an indication of insufficient
geopolymerisation or excess alkali. Further investigation into the materials showed
that the efflorescence was composed of sodium, oxygen and phosphorus. XRF analysis
also showed that the precipitate showed clear presence of sodium phosphate hydrate
(Na3PO4.12H2O) in all samples ambient cured. Figures 4.4 and 4.5 below show the
efflorescence forming on the outside of Mix One at 14 and 28 days respectively.

Figure 4.4: Efflorescence Formed on the Outside of Cylinders ‐ Mix One at 14 days
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Figure 4.5: Efflorescence on the Outside of Cylinders ‐ Mix One at 28 days

4.3.2 The Use of Silica Fume to Aid Ambient Curing

Table 4.3: Mix Designs One and Two
MIX ONE MIX TWO

Materials kg/m3 kg kg/m3 kg
20 mm 554 36 554 36
10 mm 277 18 277 18
7 mm 462 30 462 30
Sand 554 36 554 36
Fly Ash 408 27 362 24
Sodium Silicate 103 6.7 103 6.7
Sodium Hydroxide 41 2.7 41 2.7
Silica Fume - - 46 3.0
Calcium Hydroxide - - - -
Extra Water 23 1.5 23 1.5
TOTAL 2400 157.5 2400 157.5

Mix Two was based upon using Mix One with the addition of silica fume to the mix.
Silica fume was substituted in for fly ash at a quantity of 8.3% of the geopolymer (no
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aggregate) based upon mix designs previously established in geopolymer pastes. Upon
scaling up to a concrete by addition of aggregate, the silica fume content of the mix
stood at 1.9% of the 65 litre concrete mix. Both Mix One and Mix Two were produced
on the same day.

The silica fume was the final constituent added during the mixing process in the
production of Mix Two. This was undertaken so that in the event that rapid setting
occurred upon addition, it would be obvious that the silica fume was the cause and
could be traced. This method of mixing was used consistently throughout the research.

It was observed that upon ambient curing of the first two mixes made, Mix Two (silica
fume included) experienced some expansion after 3 days above the top of the cylinder
mould as seen in Figures 4.6 and 4.7. There was no expansion of Mix One which would
suggest that this was purely an effect from the included silica fume. The expansion of
these cylinders therefore required that these cylinders be cut down to size
(approximately 200mm in length for compression specimens) in order for them to be
tested upon an even top surface for equal distribution of force throughout the
specimen. The expansion of Mix Two’s cylinders only occurred during the initial setting
when the concrete was wet. This was apparent as after the concrete had dried and
was subsequently removed from the moulds at 7 days, there was no change in
diameter of the specimens.

It was also apparent that at 3 days after pouring Mix Two had set slightly faster than
Mix One, suggesting that the silica fume did increase the rate of curing by a small
amount. Mix Two had completely set by 5 days old in comparison to Mix One being
ready at 7 days. Mix Two also exhibited an amount of efflorescence on the outside of
cylinders similar to Mix One, the amount present though was considerably less.

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Figure 4.6: Expansion of Mix Two (right) Relative to Mix One (left).

Figure 4.7: Expansion of Mix Two Cylinders
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35
30
25
20
Mix One
Mix Two
15 Mix Four
Mix Three
10
0
0 5 10 15 20 25 30

Figure 4.8: Compressive Strength for Mixes One and Two

Table 4.4: Compressive Strength of Mix Two (MPa)
MIX TWO
0 0.0 0.00 -
7 1.9 0.09 3
14 7.0 0.14 3
21 10 0.11 3
28 13 1.3 3

It can be seen from the resulting compressive strengths in Table 4.4 that the addition
of silica fume to the geopolymer mix had a negative effect on the strength. With just
1.91% of the concrete mix being silica fume substituted for fly ash, the final strength of
the concrete mix more than halved. The 28 day strength of Mix Two peaked at only 13
MPa in comparison to Mix One’s 30 MPa with no silica fume. The strength
development curve can be seen to have diminished after 14 days and have no
significant growth after 28 days (Figure 4.8).
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The difference in compressive strengths between Mix One and Two can be explained
through the extra amount of silicon present in Mix Two. The inclusion of silica fume
combined with the already present sodium silicate presented an abnormal amount of
silicon in the mix. It would be seen that silica fume particles have not reacted within
the microstructure of the geopolymer, and are present in the concrete, un‐reacted.
The resulting compressive strength of Mix Two was unexpected, as it had set faster
than Mix One and a higher strength was therefore predicted, particularly at 7 days
after curing.

This is in contrast to the findings of Barbuiya et al (2009) who discussed that upon the
addition of silica fume to cement based concrete, the fine particles of the silica fume
combine with the concrete transition structure. This is known as the ‘micro‐filler
effect’ upon which the material’s structure is strengthened with the transitional bonds
between particles. It was discovered that an addition of silica fume at a quantity of 5%
of the concrete increased the strength by approximately 20%.

It can therefore be seen that the addition of silica fume to geopolymer concrete at a
quantity of 8.3% of the geopolymer poses a negative effect on the final strength. With
this composition of silica fume replacing fly ash, the final strength is more than halved.
Further to this, the concrete specimens experience a swelling above the top of the
cylinder moulds, something that would not be suitable in an industrial concrete
application.

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4.3.4 The Effect of Free Water Content on the Strength of

Geopolymer Concrete
Table 4.5: Mix Design Four
MIX FOUR
Materials kg/m3 kg
20 mm 554 39
10 mm 277 19
7 mm 462 32
Sand 554 39
Fly Ash 408 29
Silica Fume - -
Calcium Hydroxide - -
Extra Water - -
TOTAL 2400 168.0

An investigation into the effect of raising the free water content of a geopolymer
concrete mix was carried out. This undertaken research was required to distinguish
between the method of producing geopolymer paste and concrete. The included
aggregate in the concrete holds water and therefore a workable concrete mix can be
made without the addition of any extra water to the mix.

Avoiding this condition can be achieved by preparing the aggregate in Saturated
Surface Dry condition. This was not carried out in an attempt to keep the research
relevant to large scale concrete production, in which it would not be efficient to
prepare large quantities of aggregates to SSD. It is also a difficult stage to get to, as it
is based on visual and touch parameters, however it can be complied with by
Australian Standard 1141.5‐2000 and 1141.6.1‐2000. The concept of preparing
aggregate to SSD is that the particles appear damp, but upon surface touching no
moisture is felt and therefore would occur differently upon individual opinion. This
condition is optimum for concrete preparation in order to yield aggregate that is
holding enough moisture only to a point where it is not surface wet, and therefore not
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contributing any water to the mix. The moisture of these particles also prevents any of
the added free water to the concrete mix being absorbed by the dry aggregate too.

The water content of the mix is contributed to by the condition of the aggregate, any
extra water added to the mix, and the water used in the alkaline solution. In Mixes One
and Two, it was found that the free water content was approximately 4.0 litres over a
65 litre mix of concrete, including 1.5 litres of extra added water, producing a 2.6%
free water content as seen in Table 4.6. By using aggregate that was not prepared in
any situation obtaining it straight from the outside conditions under the rain, Mix
Four’s water content was raised to 4.2% after calculating 6.5 litres of free water in the
aggregate and alkaline solution as seen in Table 4.7.

Prior to mixing, it was anticipated that the strength of this mix with the higher free
water content would be lower than Mix One. This is the situation as seen in ordinary
Portland cement concrete, as raising the water content lowers the ultimate strength.

Table 4.6: Free Water Content of Mix One
MIX ONE
Water Mass of Water
Aggregate
20mm 0.45 36 0.16
10mm 0.69 18 0.12
7mm 1.64 30 0.49
Sand 0.42 36 0.15
Added Water 1.5
Total Free Water
Content (kg)
4.0
Total Free Water
Content (%)
2.6
f'cm.28 (MPa) 30
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Table 4.7: Free Water Content of Mix Four
MIX FOUR
Water Mass of Water
Aggregate
20mm 1.25 36 0.45
10mm 1.50 18 0.27
7mm 4.14 30 1.24
Sand 8.17 36 2.94
Added Water 0
Total Free Water
Content (kg) 6.5
Total Free Water
Content (%) 4.2
f'cm.28 (MPa) 11

Mix Four (investigating a mix with a higher water content) was designed exactly the
same as Mix One poured earlier in the year. No preparation of the aggregates was
carried out as these were obtained straight from the storage area, that was exposed to
heavy rain that week, into sealed bins to retain the water content at that time.

It was noticed that the water in the mix had an effect on the appearance of the
geopolymer concrete. The concrete had an oily appearance with black portions spread
throughout where the excess water was sitting in the mix. Figure 4.9 below shows an
example of this on top of a poured cylinder during the placement. These black sections
disappeared as the concrete set. This oily appearance was seen consistently over all
further mixes produced with this high free water content throughout the year.

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Figure 4.9: Excess Water in Geopolymer Concrete

Obviously, when mixed the concrete was exceptionally easy to place with the high
water content and the mix had a high slump value of over 250mm. Due to the high
slump nature of this mix, only a light amount of vibration was applied to the cylinders
to avoid segregation of the mix and letting all the aggregate fall to the bottom of the
moulds and therefore producing more of a paste at the top of the cylinder.

Understandably, Mix Four took quite some time to set. At 7 days old it was seen that
the concrete still may not have set properly, as the strength at this time was even
lower than expected, with a 2.5 MPa average in comparison to Mix One’s 8.6 MPa. Mix
Four only had specimens taken for 7 and 28 days old in compression, and 28 days for
tensile. Therefore, the strength development and rate of changes cannot be observed
as closely over 28 days.

The final strength of Mix Four did not get close at all to Mix One as seen in Figure 4.10.
At 28 days the compressive strength of concrete reached 10.8 MPa (Table 4.8). It can
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therefore be seen that by increasing the free water content in a geopolymer mix to
almost double, it effectively reduces the 28 day strength to a third of the original mix.

Table 4.8: Compressive Strength of Mixes One and Four (MPa)
MIX FOUR
0 0.0 0.00 -
7 2.5 0.09 3
28 11 0.48 3


35
30
25
20
Mix One
Mix Two
15 Mix Four
Mix Three
10
0
0 5 10 15 20 25 30

Figure 4.10: Compressive Strength of Mixes One and Four

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4.3.3 The Use of Calcium Hydroxide to Aid Ambient Curing

Table 4.9: Mix Design Three
MIX THREE
Materials kg/m3 kg
20 mm 554 36
10 mm 277 18
7 mm 462 30
Sand 554 36
Fly Ash 380 25
Silica Fume - -
Calcium Hydroxide 28 1.8
Extra Water - -
TOTAL 2400 156.0

Calcium hydroxide (hydrated lime) is used in common concrete applications to shorten
the setting time under ambient conditions. Similar to Mix Two, calcium hydroxide was
substituted into Mix Three for fly ash, at an amount of 5% of the geopolymer mix. This
replacement of fly ash therefore worked out to 27.6 kg/m3 for the total concrete mix.

Mix Three was poured at the end of July, 2009 with the intention of developing a faster
setting ambient cured geopolymer concrete with a higher early strength. The calcium
hydroxide was added to the concrete mix in much the same fashion as the silica fume
in Mix Two, in that it was the final constituent included in the mixing procedure.

Due to the high moisture content of the aggregates used, the concrete mix was
extremely wet during mixing. At this point it would be thought that placement of the
concrete would be easier than in previous experiments, although the final strength of
the concrete would be lower. The slump recorded of this mix exceeded 250mm, similar
to Mix Four.

Upon addition of the calcium hydroxide to the mix and then mixing, it was seen that
the concrete was bubbling furiously as the reaction between the chemicals in the fly
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ash and the calcium hydroxide. At this point it was realized that something never
experienced by the author was occurring so progress was made as quick as possible to
place the concrete into the moulds.

Approximately ten minutes into placement of the concrete in the moulds, rapid setting
began to occur and placement of the mix became very difficult. Vibration of the
cylinders did not have an effect on the form of the concrete, and air voids remained in
some of the cylinders. Because the concrete was set on the day of casting, de‐
moulding of the cylinders was carried out at only two days of age. Upon removing the
concrete from the moulds it was apparent that majority of the compression cylinders
turned out fine for testing as usual. The tensile cylinders on the other hand, appeared
to have a considerable amount of voids in them because of the fast setting concrete,
however testing of these cylinders was still carried out in order to yield some data for
this mix (Figure 4.12).

Mix Three and Four were produced on the same day and therefore had the same
relatively high free water content. Mix Four, as explained in the previous section of this
report, is a standard geopolymer concrete mix investigating the effect of high water
content. For this reason, Mix Three and all further mixes later on in the year were
compared to Mix Four. The strength of Mix Three was consistently stronger than the
reference mix throughout, and the rate of strength development was substantially
larger up until 14 days of age. Eventually, though, the strength development of Mix
Three tapered off and did not exhibit any rapid strength gain within 28 days. The final
testing at 28 days showed a compressive strength of 18 MPa, comparative to Mix Four
which exhibited a 28 day strength of 11 MPa as seen in Table 4.10 and Figure 4.11.

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Table 4.10: Compressive Strength of Mix Three
MIX THREE
0 0.0 0.00 -
7 9.2 0.78 3
14 15 0.25 3
21 17 0.33 3
28 18 0.3 3


20
18
16
14
12
Mix One
10
Mix Two
8 Mix Four
Mix Three
6 Mix Five
Mix Six
4 Mix Seven
0
0 5 10 15 20 25 30

Figure 4.11: Compressive Strength of Mixes Three and Four

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Figure 4.12 : Rapid Setting Effects and Efflorescence on Mix Three Cylinders

Figure 4.13: Cross Section of Small Cylinder ‐ Mix Three
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Figure 4.13 shows the cross section of a cylinder from Mix Three. The most obvious
aspect is the shape of the top (right side of the image) where the concrete had set just
as the cylinder had been filled up. The material at the top of these cylinders was flaky
and brittle and so each affected cylinder had this surface condition trimmed off prior
to testing. Another aspect of this cylinder is the amount of air voids seen throughout
the section. Because Mix Three set whilst the cylinders were being vibrated all of the
air voids were not able to be removed from the concrete.

It should however be noted, that any results obtained from the testing of these
specimens provide little use in further applications of geopolymer concrete mix design.
It is recommended that the research in the addition of calcium hydroxide is continued
with varying amounts added. On a larger scale in industry the time for placement of
concrete would be much longer, and therefore setting would occur before all concrete
is put into place. However, for the purpose of this research, the strength development
is to be investigated into the addition of calcium hydroxide to geopolymer concrete, so
testing of the cylinders continued.

As seen in Figure 4.12 Mix Three also exhibited an amount of efflorescence on the
outside of the cylinders. It was apparent at this stage that all geopolymer concrete
samples cured under ambient conditions consistently exhibited this property.

Approximately a week later, it was informed to the author of this report, that the
Physics department at Curtin University had attempted to replicate the rapid setting
nature of this mix by producing a geopolymer paste mix with the same proportions as
Mix Three, albeit without the aggregate. The outcome, however, differed in that the
mix did not rapid set whilst preparing and in fact took approximately 36 hours before it
had properly set (M. Lee, personal communication August 26, 2009).

To further the research into the effect of adding calcium hydroxide to geopolymer
concrete, Mixes Five, Six and Seven were produced with varying amounts of the
product added. The difference in this mix was the calcium hydroxide was added to a
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set mix as an addition, not through substitution for fly ash. This was achieved by
producing a replica of Mix Four (standard geopolymer concrete mix, with high water
content, as was Mix Three) and adding the hydrated lime at a percentage by mass of
the geopolymer paste in the concrete. Quantities of 0.5%, 1% and 3% of the
geopolymer were added to the concrete mix respectively. Table 4.11 below shows the
specific mix designs of these mixes. It can be seen that the total composition of Mixes
Five to Seven exceed a composition of 2400 kg/m3 due to the extra water and calcium
hydroxide added to the already complete concrete mix. The amount of water added
was calculated in order to yield the same free water content as Mixes Three and Four.

Table 4.11: Mix Designs Five, Six and Seven
MIX FIVE MIX SIX MIX SEVEN
Materials kg/m3 kg kg/m3 kg kg/m3 kg
20 mm 554 5.5 554 5.5 554 5.5
10 mm 277 2.8 277 2.8 277 2.8
7 mm 462 4.6 462 4.6 462 4.6
Sand 554 5.5 554 5.5 554 5.5
Fly Ash 408 4.1 408 4.1 408 4.1
Sodium Silicate 103 1.0 103 1.0 103 1.0
Sodium Hydroxide 41 0.4 41 0.4 41 0.4
Silica Fume - - - - - -
Calcium Hydroxide 2.8 0.03 5.5 0.1 17 0.2
Extra Water 96 1.0 96 1.0 96 1.0
TOTAL 2499 25.0 2502 25.0 2513 25.1

In order to avoid quick setting mixes hardening in the pan, the bulk standard mix
design was produced and then the required amount for each sub‐mix (Mixes Five, Six
and Seven) was placed onto an aggregate preparation tray. From here the varying
amounts of calcium hydroxide was added and then mixed by hand into the concrete.
This also allowed for a better feel of the workability of the mix, as any quick setting
could be detected straight away.

Mix Five (0.5% calcium hydroxide) presented no difference in workability or immediate
setting time whilst mixing compared to Mix Four. In order to make the required
amount of concrete for 6 compression cylinders (3 x 7 days, 3 x 28 days), only 29 grams
of calcium hydroxide was added to 25 kilograms of concrete. In the time it took to mix
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in the calcium hydroxide and then transfer the concrete into the cylinders, Mix Five
appeared to have no difference in workability relative to any standard geopolymer mix
prepared earlier in the year. After 24 hours of curing it was apparent that Mix Five had
still not set. Complete setting occurred by 5 days after pouring, very similar to a
standard geopolymer concrete mix with no additives.

Mix Six (1% calcium hydroxide) exhibited a slightly faster setting rate than Mix Five
during the day. An amount of 58 grams of calcium hydroxide was added to the
concrete mix and whilst there was no noticeable setting or difference in workability
during placement, approximately two hours after producing the mix it was clear that it
had begun setting. Figure 4.14 below shows the excess of Mix Six at two hours after
mixing and partially set. At this point the concrete was beginning to harden on the top,
however beneath the surface it was still very wet. By 3 days of curing Mix Six had
completely set and was able to be removed from the moulds.

Figure 4.14: Mix Six at Two Hours after Pouring

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Mix Seven (3% calcium hydroxide) was the only mix prepared out of the last three
which exhibited noticeable early setting properties during placement of the concrete.
It was experienced that whilst combining the 173 grams of calcium hydroxide that the
workability of the concrete changed almost instantly, however not enough to affect
the placement. The mix felt heavier to move after mixing in the calcium hydroxide as it
appeared the reaction between the chemicals in the concrete had occurred
immediately. The rate of reaction was not as quick as Mix Three though, where the
concrete set before all cylinders could be poured, and therefore the placement of Mix
Seven went accordingly to plan.

Again, the left over concrete from Mix Seven was kept to observe how long it took to
set compared to Mix Six. After just one hour Mix Seven was significantly harder than
Mixes Five and Six, and was obviously going to be completely set within hours. Figure
4.15 below shows the condition of the excess from Mixes Six and Seven after one hour
of setting, and it can be seen that Mix Six is still completely wet where as Mix Seven is
significantly further along in the setting process. After twelve hours of standing after
pouring, Mix Seven had completely set and therefore the cylinders would have been
able to be de‐moulded after 24 hours.

Figure 4.15: Mixes Seven (Left) and Six (Right) at One Hour after Pouring
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The relatively low final strength’s of Mixes Five, Six and Seven came as quite
unexpected due to the setting times experienced by the three mixes. Though Mix Five
set in the same amount of time as the reference mix, it was expected that a small
amount of calcium hydroxide would have a compressive strength slightly higher, if not
equal to the reference Mix Four. The faster setting nature of Mixes Six and Seven made
for the prediction of higher compressive strengths in proportion to the amount of
calcium hydroxide used. Despite this, the highest compressive strength experienced by
these three mixes was 11.0 MPa, only slightly higher than the 10.8 MPa reference as
seen below in Figure 4.16.


12
10
Mix One
6
Mix Two
Mix Four
Mix Three
4
Mix Five
Mix Six
Mix Seven
2
0
0 5 10 15 20 25 30

Figure 4.16: Compressive Strength of Mixes Five, Six and Seven (MPa)

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Table 4.12: Compressive Strength of Mixes Five, Six and Seven (MPa)

7 3.2 0.10 3
MIX FIVE
28 7.4 0.33 3
7 3.6 0.37 3
MIX SIX
28 8.0 0.81 3
7 5.1 0.10 3
MIX SEVEN
28 11 0.89 3

It can be seen from the results in Table 4.12 that the compressive strength of
geopolymer concrete increases in proportion to the amount of calcium hydroxide used
within the mix. Mix Seven with a 3% calcium hydroxide addition exhibited a slightly
higher compressive strength than Mixes Five and Six. The difference though is seen at
the 7 day strengths where any addition of calcium hydroxide to a geopolymer concrete
mix increases the strength and rate of setting, making the mix applicable for use in
industry applications where the concrete is cured without the use of steam rooms.

Mix Seven appears to be a practical solution to developing a geopolymer concrete mix
that sets within 24 hours without decreasing the final strength. The addition of calcium
hydroxide at an amount of 3% of the geopolymer provides a concrete mix that will set
efficiently without the need for a steam room, and provide a final strength to that of
equal to a mix without any additives. If Mix Seven had achieved a final compressive
strength substantially higher than the reference mix, it would be seen that this was the
optimum arrangement for the inclusion of calcium hydroxide in geopolymer concrete.

Another aspect of these three mixes that was noticed is how quickly the efflorescence
began to appear after de‐moulding. Approximately 30 minutes after all cylinders were
removed from their moulds, a small amount of efflorescence started to appear around
the top of the cylinders below where any excess bits of concrete had been chipped off
during handling. Figure 4.17below shows the first amounts of efflorescence appearing
at half an hour after de‐moulding the cylinders at five days after casting.
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It was interesting to discover the substantial difference between a 3% addition of
calcium hydroxide relative to the 5% replacement of fly ash as seen in Mix Three.
Despite the fact that Mix Three was deemed a failure, the compressive strengths of the
unaffected cylinders were still substantial. From this, it would be seen that
incorporating a 3% replacement of fly ash with calcium hydroxide would produce a mix
that sets within 12 hours and presents positive compressive and tensile strengths.

Figure 4.17: Efflorescence Beginning to Form after De‐moulding ‐ Mix Five

4.4 Indirect Tensile Strength of Geopolymer Concrete

The relationship between the compressive strength and indirect tensile strength of
concrete is well known. Whilst not as heavily relied upon from the results point of
view, the tensile strength of the tested specimens must also be analysed to gain a full
perspective of the conclusions. The tensile strength of these specimens was tested in
compliance with Australian Standard 1012.10‐2000.
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The indirect tensile tests were only carried out on Mix One to Four due to both
material and time restraints. To undertake this, cylinders were produced using 150mm
diameter by 300mm long moulds. The tensile splitting strength was determined in
accordance with Australian Standards AS1012.10‐2000: Method of testing concrete –
Determination of indirect tensile strength of concrete cylinders (Brasil or splitting test).

From the determined splitting load P (kN), it is possible to determine the indirect
tensile strength in MPa by the following equation:
T = 2000P / πLD
Where P = Splitting strength of cylinder in kN.
L = Length of cylinder in mm
D = Diameter of cylinder in mm.
T = Tensile Strength in MPa

For the most part the indirect tensile strength of the four mixes were proportional to
the compressive strength, with Mix One and Three being the strongest easily (2.7 MPa
and 2.2 MPa respectively), and Mix Two and Four trailing behind. Mix Four (2.0 MPa) in
fact was quite a bit stronger in tension than Mix Two (1.5 MPa) in contrast to the
compressive strength of these two mixes in which the two mixes were extremely
similar, Mix Two being just slightly stronger as seen in Figure 4.18.

Due to time and material restraints again, Mix Four only had tensile cylinders cast for
one day of testing. For this reason, the tensile strength development shape of the mix
cannot be viewed and therefore is shown on the below figure by just a marking at 28
days old.

It can be seen that the magnitude of tensile strength of geopolymer concrete at early
stages in the curing life is a fairly good indicator of its later strengths relative to other
mix designs. The ranking of strongest to weakest mix at 14 days old is the same at 28
days after casting. This is in contrast to compressive strength, which can change order
as age increases. This can be seen particularly in Figure 4.1 where the strength of Mix
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Three was higher than Mix One at 7 days, but that soon changes as Mix Three tapers
off very early.

3
Tensile Strength of Geopolymer Concrete (MPa)
2.5
Tensile Strength (MPa)
1.5 Mix One
Mix Two
Mix Three
Mix Four
1
0.5
0
0 5 10 15 20 25 30

Figure 4.18: Indirect Tensile Strength of Mixes One to Four

Table 4.13: Indirect Tensile Strength of Mixes One to Four
TENSILE STRENGTH
Age Mix One Mix Two Mix Three Mix Four
14 days 2.0 0.95 1.6 -
28 days 2.7 1.5 2.2 2.0

Lloyd and Rangan (2009) suggest that it is possible to draw a relationship between the
tensile and compressive strengths of geopolymer concrete. Over a period from 2007
and 2008, a variety of mix designs were tested at Curtin University and had their
results used to develop this association. It was discovered that over 41 tests, the
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relationship between the compressive and tensile strengths of geopolymer concrete
was:

Fct = 0.6 ± 0.1√fcm

Neville (2000) suggested that a similar relationship can be drawn between the tensile
and compressive strength of ordinary Portland cement based cements. This
relationship was as follows:

Fct = 0.3 fcm⅔

These relationships were tested with the results obtained through the research for this
report. The results are presented below in Table 4.14.

Table 4.14: Relationship Between Compressive and Tensile Strength
fct MPa
(Lloyd fct MPa
Age (days) fcm MPa and (Neville fct MPa
Rangan 2000)
2009)
MIX ONE 14 17.3 1.0 2.0 2
28 30 1.1 2.9 2.7
MIX TWO 14 7.0 0.87 1.1 0.95
28 12.8 0.96 1.6 1.5
MIX THREE 14 14.9 0.97 1.8 1.6
28 18.2 1.0 2.1 2.2
MIX FOUR 28 10.8 0.93 1.5 1.4

As can be seen, the estimation for the relationship between tensile and compressive
strengths for the research carried out here is much suited towards Neville’s
suggestion. The relationship that Lloyd and Rangan suggested did not present very
similar findings to the present research, which is unexpected considering it has been
specifically developed from geopolymer concrete specimens. A possible reason for this
though is that it is stated in the report that all utilized concrete mixes were cured in
the steam room under varying temperatures and regimes. Under the research carried
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out for this relationship, no such investigation was carried out with specimens cured

under ambient conditions as in the research for this present report.

At this stage with only four mix designs and 7 values tested, an initial estimation into
the relationship between the compressive and tensile strengths of geopolymer
concrete cured under ambient conditions would suggest that Neville’s suggestion is
valid.

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5. SUMMARY AND CONCLUSIONS

5.1 Introduction

Chapter 5 presents a summary of the present study, the major conclusions from the
conducted research.

The main objective of this study was to further the past research carried out in
geopolymer concrete mix design and develop a scaling up process of work carried out
by the Physics Department at Curtin University, in which they produced geopolymer
pastes that set quicker under ambient conditions. By adding aggregate to these mixes
and therefore producing a geopolymer concrete, several mix designs were tested by
introducing different additives to the concrete. The two processes differed by more
than just adding aggregate, as it was discovered that the longer handling time of the
concrete restricted the effectiveness in adding calcium hydroxide to geopolymer
concrete. It was also apparent how much water is stored within the aggregate, as no
extra water needed to be added to the mix at all, due to how wet the aggregate was in
Mixes Three to Seven.

In order to maintain a constant approach between each of the batches, mixing
procedures, materials used and mix designs for the most part were kept constant.

5.2 Production of Geopolymer Concrete

5.2.1 Pre-production Issues

The most important work carried out before the mixing of the concrete was the
preparation of the alkaline liquid. This liquid was a combination of a sodium hydroxide
solution and sodium silicate. The sodium hydroxide solution was formed by dissolving
pellets into distilled water under pre‐calculated proportions. Upon carrying out this
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dissolution it was seen that the reaction carried out was exothermic, and heat was
generated as the solid dissolved.

Sodium silicate was used as obtained through a local supplier. These two elements
were combined at the beginning of the day of mixing and kept sealed until use. The
sodium hydroxide solution though was able to be produced a few days prior to mixing
so long as any precipitate formed in that standing time was re‐dissolved again before
use. No super plasticisers were used in the laboratory work in this research.

Aggregates were not prepared prior to use to provide a realistic comparison to that of
a larger scale in industry. The water content of the aggregates were taken, though, and
noted what effect this content had on the final results.

5.3 Results and Observations

5.3.1 The Use of Silica Fume to Aid Ambient Curing

The addition of silica fume to geopolymer concrete produced a faster setting mix;
however it had a negative effect on the compressive and tensile strength. In this mix,
silica fume was added at a quantity of 8.3% of the geopolymer paste as a replacement
for fly ash. The 28 day compressive strength for Mix Two peaked at 12.8 MPa
comparative to Mix One’s 30.0 MPa (Figure 4.8).

The addition of this silica fume to the concrete mix also caused a swelling of the
cylinder, resulting in a porous expansion above the top of the mould upon setting as
seen in Figures 4.6 and 4.7.

5.3.2 The Effect of Free Water Content on Geopolymer Concrete

It was seen that under ambient conditions in the middle months of the year in Western
Australia, the curing of standard geopolymer concrete with no additives takes almost a
week, therefore preventing any testing to be undertaken before an age of 7 days.
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The effect of raising the free water content in geopolymer concrete was similar to that
of ordinary concrete, reducing its strength. This was confirmed in Mix Four, where by
doubling the free water content of Mix One, the 28 day strength resulted in one third
of it with 10.8 MPa (Figure 4.10).

5.3.3 The Use of Calcium Hydroxide to Aid Ambient Curing

The addition of calcium hydroxide within a geopolymer concrete mix causes the
concrete mix to set quicker. In the research carried out, the use of calcium hydroxide
did not improve the compressive strength of the concrete despite it setting quicker.

It can be seen in Table 4.16 that increasing the amount of calcium hydroxide into a
geopolymer concrete mix proportionally increases the compressive strength of the
concrete mix. It was seen that an addition of 3% of the geopolymer of calcium
hydroxide produced a concrete mix that set within 24 hours and exhibited a
compressive strength extremely similar the standard reference mix (11.0 MPa). It was
also seen that 0.5% and 1% of calcium hydroxide added in fact decreased the
compressive strength of the mix (Figure 4.16).

Upon replacement of 5% of fly ash with calcium hydroxide in a geopolymer mix, the
concrete flash set at approximately 10 minutes into placing the concrete into moulds.
It was also seen that the chemicals in the mix were furiously reacting after thorough
mixing in of the calcium hydroxide. Though the strength of Mix Three (5% calcium
hydroxide utilized) substantially higher than the reference strength, it was seen as a
failed mix because of the rapid setting and therefore would not be applicable in large
scale operations (Table 4.10).

5.3.4 Other Observations During Research

During this research, all ambient cured geopolymer concrete specimens developed a
layer of efflorescence on the outside as seen in Figures 4.4 and 4.5. This efflorescence
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is thought to be unreacted sodium hydroxide in a white crystalline form (Temuujin, van
Riessen and Williams 2009). This however, did not occur in the experimental research
carried out in the steam curing of geopolymer concrete specimens.

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6. RECOMMENDATIONS

To further develop the application of geopolymer concrete for structural use, research
needs to be continued in order to refine the knowledge attained on the properties of
this material. The research carried out for this report extends to only a very limited
scope of the variables that were suggested for investigation. Because of both material
and time restraints, a number of variables were not tested, however the following
points are recommendations to be investigated in further research on geopolymer
concrete mix design.

1. As can be seen by the shape of Mix One’s strength vs. age graph in Figure 4.3,
the strength development of geopolymer concrete extends for a period beyond
28 days. The next step would be to investigate the strength development of
geopolymer concrete for long term periods after pouring. The comparison of
the final strength of geopolymer concrete comparative to the strength
development of OPC concrete would promote the use of it in long term
applications.

2. Past research has shown that the addition of silica fume in concretes with fly
ash aid the strength after ambient curing. Similar to the method carried out in
this report for calcium hydroxide, it is worth investigating the optimum
quantity of silica fume required in a geopolymer concrete mix that allows a
quicker setting time and a higher early strength of the concrete.

3. Mix Three showed promising results with the addition of calcium hydroxide to
the concrete, but unfortunately did not allow enough time to complete the
pour before it set. A possible solution into this could be the use of super
plasticiser in the mix. This will increase the setting time of the mix and
therefore hopefully provide a delay prior to rapid setting occurring. The super
plasticiser would be added, though, not as a final additive like the calcium
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hydroxide, but as part of the alkaline liquid prior to mixing with the dry
materials.

4. Mix Four was used to investigate whether raising the free water content of a
geopolymer concrete lowered the strength of the mix, as is the case with
ordinary Portland cement based concrete. The free water content between the
two compared mixes differed greatly, and therefore producing a mix with a
water content between Mix One and Four would establish whether any type of
linear relationship exists within this variable.

5. To follow on from Lloyd and Rangan’s (2009) research for the relationship
between compressive and tensile strengths, further investigation into this
relationship could be considered for ambient cured geopolymer concrete. An
initial investigation into this has been carried out in this report, however only
four mixes were tested for tensile strength due to material and time
constraints. Lloyd and Rangan only developed this relationship for geopolymer
concrete specimens under steam curing.

6. An initial aim for this thesis was to investigate the use of a bayer liquor residue
to produce a geopolymer concrete mix, which was unfortunately not carried
out due to time restraints. Bayer liquor is a waste material that is produced in
the bauxite removal stage in the production of alumina. The Centre of
Materials Research at Curtin has previously used this material to produce a
geopolymer paste in small quantities. Scaling this exercise up to produce a
concrete mix with the bayer would provide a largely sustainable option in using
a concrete that is comprised of fly ash and bayer, two industrial waste
products.

7. Further to this, once the transition of bayer liquor in a geopolymer paste to
concrete has been made, the next step in a sustainability exercise would be to
investigate what amount of the conventionally made alkaline solution can be
directly replaced with the bayer. This would not only increase the sustainability
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view of the concrete, in using large amounts of waste, but an economic benefit
could be established in negating the need to dispose of this material. Elemental
composition of the concrete obviously matters, but by progressively increasing
the amount of bayer in the mix, which replaces the costly sodium hydroxide
and sodium silicate, economic and environmental advantage could be had.

8. The effect of adding calcium hydroxide to a geopolymer concrete mix was
investigated in Mixes Three, Five, Six and Seven. However, due to the
conditions in which the aggregates were kept, each of these mixes ended up
with a substantially high water content in order to keep a viable comparison.
Mixes Three (5% calcium hydroxide) and Seven (3% calcium hydroxide)
exhibited the largest compressive strength, yet was limited through the high
water content. It is worth reproducing these mixes with a lower water content
to investigate just how well this product works in geopolymer concrete.
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APPENDIX A
Mix Design Details of Carried Out Geopolymer Concrete Mixes

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MIX ONE MIX TWO MIX THREE MIX FOUR MIX FIVE MIX SIX MIX SEVEN
Materials kg/m3 kg kg/m3 kg kg/m3 kg kg/m3 kg kg/m3 kg kg/m3 kg kg/m3 kg
20 mm 554 36 554 36 554 36 554 39 554 5.5 554 5.5 554 5.5
10 mm 277 18 277 18 277 18 277 19 277 2.8 277 2.8 277 2.8
7 mm 462 30 462 30 462 30 462 32 462 4.6 462 4.6 462 4.6
Sand 554 36 554 36 554 36 554 39 554 5.5 554 5.5 554 5.5
Fly Ash 408 27 362 24 380 25 408 29 408 4.1 408 4.1 408 4.1
Sodium Silicate 103 6.7 103 6.7 103 6.7 103 7.2 103 1.0 103 1.0 103 1.0
Sodium Hydroxide 41 2.7 41 2.7 41 2.7 41 2.9 41 0.4 41 0.4 41 0.4
Silica Fume - - 46 3.0 - - - - - - - - - -
Calcium Hydroxide - - - - 28 1.8 - - 2.8 0.03 5.5 0.1 17 0.2
Extra Water 23 1.5 23 1.5 - - - - 96 1.0 96 1.0 96 1.0
TOTAL 2423 157.5 2423 157.5 2400 156.0 2400 168.0 2499 25.0 2502 25.0 2513 25.1

Compressive Strength of Mix Designs (MPa)
Age (days) 7 14 21 28
MIX ONE 8.6 17 24 30
MIX TWO 1.9 7 10 13
MIX THREE 9.2 15 17 18
MIX FOUR 2.5 - - 11
MIX FIVE 3.2 - - 7.0
MIX SIX 3.6 - - 8.0
MIX SEVEN 5.1 - - 11

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APPENDIX B
Details of Geopolymer Concrete Cylinder Testing

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Mix One Standard geopolymer reference mix

COMPRESSION
Mass (g) Length (mm Diam (mm) Area (mm2) Force (kN) Stress (Mpa)
7 day 9th June 2009
7 day - 1 3960 205.1 99.5 7776 68.7 8.835
7 day - 2 4044 205.3 100 7854 66.8 8.505
7 day - 3 3994 204.7 99.8 7823 65.6 8.386
Average 8.576
14 day 16th June 2009

14 day - 1 3972 205.6 99.6 7791 131.1 16.8
14 day - 2 3968 203.7 99.6 7791 131 16.8

14 day - 3 3989 204.3 100.0 7854 143.0 18.2
Average 17.3
21 day 23rd June 2009

21 day - 1 3947 198.4 100.4 7917 190.2 24.0
21 day - 2 3936 203.8 99.5 7776 191.5 24.6
21 day - 3 3962 205 100.1 7870 194.3 24.7
Average 24.4

28 day - 1 3990 205.1 100.2 7885 234 29.7
28 day - 2 3934 203.4 99.8 7823 236.9 30.3
28 day - 3 3957 203.8 99.6 7791 233.3 29.9
Average 30.0
TENSION
14 day - 1 13008 300.5 149.9 17648 141.2 2.0
14 day - 2 13061 300 149.8 17624 140.6 2.0
14 day - 3 13034 300 149.8 17624 137.9 2.0
Average 2.0

28 day - 1 12916 301 149.6 17577 182 2.6
28 day - 2 12957 300.5 150.1 17695 194.4 2.7
28 day - 3 12977 300 150.2 17719 191.8 2.7
Average 2.7
MIX ONE
Materials kg/m3 kg %
20 mm 554.4 36.0 23.1
14 mm 277.2 18.0 11.6
7 mm 462 30.0 19.3
Sand 554.4 36.0 23.1
Fly Ash 408 26.5 17.0
Sodium Silicate 103 6.7 4.3
odium Hydroxide 41 2.7 1.7
Extra Water 23.1 1.5 1.0
Silica Fume 0 0.0 0.0
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Mix Two 8.3% silica fume fly ash replacement, cut - poured 2nd June 2009
COMPRESSION
7 day 9th June 2009
7 day - 1 3816 203.7 100 7854 15.7 2.0
7 day - 2 3806 202.7 100.1 7870 15.9 2.0
7 day - 3 3771 202.7 99.7 7807 14.2 1.8
Average 1.9

14 day - 1 3813 203.3 99.8 7823 53.5 6.8
14 day - 2 3813 203.9 100 7854 56.5 7.2
14 day - 3 3792 201.4 99.3 7744 54.4 7.0
Average 7.0
21 day 23rd June 2009

21 day - 1 3972 201.2 99.6 7791 79.4 10.2
21 day - 2 3731 200.7 100.8 7980 80.5 10.1
21 day - 3 3820 202.3 100.3 7901 81.9 10.4
Average 10.2

28 day - 1 3771 202.4 100 7854 103.3 13.2
28 day - 2 3880 202 100.7 7964 113.4 14.2
28 day - 3 3820 202.1 100.4 7917 87.8 11.1
Average 12.8
TENSION
14 day - 1 12977 306.5 149.9 17648 66.9 0.9
14 day - 2 12989 307 149.8 17624 69.3 1.0
14 day - 3 13048 308 150.2 17719 69.2 1.0
Average 0.9

28 day - 1 12910 306 149.7 17601 105.7 1.5
28 day - 2 13005 310 150 17671 111.2 1.5
28 day - 3 12914 311 149.7 17601 103.8 1.4
Average 1.5
MIX TWO
20 mm 554.4 36.0 23.1
14 mm 277.2 18.0 11.6
7 mm 462.0 30.0 19.3
Sand 554.4 36.0 23.1
Fly Ash 362.2 23.5 15.1
Sodium Silicate 103.0 6.7 4.3
odium Hydroxide 41.0 2.7 1.7
Silica Fume 45.8 3.0 1.9
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Mix Three 5% calcium hydroxide, fly ash replacement - poured 27th July 2009
COMPRESSION
7 day 3rd August 2009
7 day - 1 3.832 200.2 100.1 7870 77.2 9.8
7 day - 2 3.906 204.2 99.9 7838 75.5 9.6
7 day - 3 3.784 200 99.7 7807 63.1 8.1
Average 9.2
14 day 10th August 2009

14 day - 1 3.770 201.1 100 7854 117.4 14.9
14 day - 2 3.822 201.2 99.9 7838 118.9 15.2
14 day - 3 3.772 200.2 100.0 7854 114.4 14.6
Average 14.9

21 day - 1 3.771 198 99.9 7838 131.3 16.8
21 day - 2 3.801 201.6 100.3 7901 137.8 17.4
21 day - 3 3.531 188.2 99.4 7760 129.8 16.7
Average 17.0

28 day - 1 3.697 196 99.7 7807 142.8 18.3
28 day - 2 3.710 199.8 99.6 7791 138.4 17.8
28 day - 3 3.815 205.5 99.6 7791 144.9 18.6
Average 18.2
TENSION
14 day - 1 12.335 275 149.9 17648 111.4 1.7
14 day - 2 12.855 282 150.2 17719 101.9 1.5
14 day - 3 12.825 301 150.2 17719 113.5 1.6
Average 1.6

28 day - 1 12.611 285 149.5 17554 138.4 2.1
28 day - 2 12.841 282 149.4 17530 135.3 2.0
28 day - 3 12.222 209 149.8 17624 123.1 2.5
Average 2.2
MIX THREE
20 mm 554.4 36.0 23.1
14 mm 277.2 18.0 11.6
7 mm 462 30.0 19.3
Sand 554.4 36.0 23.1
Fly Ash 380.4 24.7 15.9
alcium Hydroxide 27.6 1.8 1.2
Extra Water 0 0.0 0.0
Darryl Hole 84
Mix Four No Silica Fume, uncut, large water content - poured 6th August 2009
COMPRESSION
7 day - 1 3.876 199.9 100.4 7917 20.8 2.6
7 day - 2 3.832 201 100.3 7901 19.2 2.4
7 day - 3 3.851 200.3 100.7 7964 19.5 2.4
Average 2.5
28 day 3rd September 2009

28 day - 1 3.726 198.4 98.5 7620 78.9 10.4
28 day - 2 3.735 199.4 99 7698 81.6 10.6
28 day - 3 3.792 199.7 99.9 7838 89.9 11.5
Average 10.8
TENSION
28 day - 1 13 298.5 149.8 17624 101.8 1.4
28 day - 2 13 301 148.9 17413 93.7 1.3
28 day - 3 13 295 150.3 17742 95.3 1.4
Average 1.4
MIX FOUR
20 mm 554.4 38.8 23.1
14 mm 277.2 19.4 11.6
7 mm 462 32.3 19.3
Sand 554.4 38.8 23.1
Fly Ash 408 28.6 17.0
Silica Fume 0 0.0 0.0

Darryl Hole 85
Mix Five 0.5% calcium hydroxide additive, poured 24th September 2009
COMPRESSION
7 day - 1 3.759 201.0 99.3 7744 25.6 3.3
7 day - 2 3.703 199.0 99.6 7791 24.1 3.1
7 day - 3 3.753 200.0 100.0 7854 24.2 3.1
Average 3.2

28 day - 1 3.636 199.2 99.0 7698 54.7 7.1
28 day - 2 3.669 199.2 100.1 7870 62.1 7.9
28 day - 3 3.683 199.8 99.1 7713 56.4 7.3
Average 7.4
MIX FIVE
20 mm 554 5.5 22.1
14 mm 277 2.8 11.2
7 mm 462 4.6 18.4
Sand 554 5.5 22.1
Fly Ash 408 4.1 16.4
Sodium Hydroxide 41 0.41 1.6
Calcium Hydroxide 2.76 0.03 0.1

Darryl Hole 86
Mix Six 1% calcium hydroxide additive, poured 24th September 2009
COMPRESSION
7 day - 1 3.755 201.0 99.6 7791 25.8 3.3
7 day - 2 3.775 200.0 99.3 7744 32.2 4.2
7 day - 3 3.783 200.0 99.7 7807 27.1 3.5
Average 3.6

28 day - 1 3.712 201.5 100.0 7854 71.4 9.1
28 day - 2 3.704 200.2 99.9 7838 60.5 7.7
28 day - 3 3.651 199.7 99.5 7776 55.7 7.2
Average 8.0
MIX SIX
20 mm 554 5.5 22.1
14 mm 277 2.8 11.2
7 mm 462 4.6 18.4
Sand 554 5.5 22.1
Fly Ash 408 4.1 16.4
Calcium Hydroxide 5.5 0.10 0.4

Darryl Hole 87
Mix Seven 3% calcium hydroxide additive, poured 24th September 2009
COMPRESSION
7 day - 1 3.753 200.2 100.1 7870 40.7 5.2
7 day - 2 3.783 201.4 99.6 7791 40.2 5.2
7 day - 3 3.761 201.2 100.2 7885 39.1 5.0
Average 5.1

28 day - 1 3.707 200.3 100.2 7885 94.4 12.0
28 day - 2 3.732 202.9 99.2 7729 75.8 9.8
28 day - 3 3.711 200.5 99.4 7760 86.1 11.1
Average 11.0
MIX SEVEN
20 mm 554 5.5 22.1
14 mm 277 2.8 11.2
7 mm 462 4.6 18.4
Sand 554 5.5 22.1
Fly Ash 408 4.1 16.4
Calcium Hydroxide 17 0.20 0.8
Darryl Hole 88

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1.3 Research Aims

This was a key point in the research, as it was important that a relevant comparison

7mm 1.64 30 0.49

Sand 0.42 36 0.15

3.4.3 Curing of Geopolymer Concrete

3.5 Testing of Concrete Specimens

4. EXPERIMENTAL RESULTS AND

Compressive Strength of Geopolymer Concrete (MPa)

Age After Pouring (Days)

4.3 Compressive Strength and Observations of Geopolymer

Compressive Strength of Geopolymer Concrete (MPa)

Age After Pouring (Days)

MIX ONE MIX TWO

Compressive Strength of Geopolymer Concrete (MPa)

Age After Pouring (Days)

4.3.4 The Effect of Free Water Content on the Strength of

Compressive Strength of Geopolymer Concrete (MPa)

Age After Pouring (Days)

4.3.3 The Use of Calcium Hydroxide to Aid Ambient Curing

Compressive Strength of Geopolymer Concrete (MPa)

Age After Pouring (Days)

Compressive Strength of Geopolymer Concrete (MPa)

Age After Pouring (Days)

Age in Compressive Standard Number of

out for this relationship, no such investigation was carried out with specimens cured

5. SUMMARY AND CONCLUSIONS

Mix One Standard geopolymer reference mix

14 day 16th June 2009

14 day - 2 3968 203.7 99.6 7791 131 16.8

21 day 23rd June 2009

28 day 30th June 2009

28 day 30th June 2009

14 day 16th June 2009

21 day 23rd June 2009

28 day 30th June 2009

28 day 30th June 2009

14 day 10th August 2009

21 day 17th August 2009

28 day 24th August 2009

28 day 24th August 2009

28 day 3rd September 2009

28 day 3rd September 2009

Mix Six 1% calcium hydroxide additive, poured 24th September 2009

28 day 3rd September 2009

Mix Seven 3% calcium hydroxide additive, poured 24th September 2009

28 day 3rd September 2009

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