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Geopolymer : Cement for low carbon economy

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TECHNICAL PAPER Special Issue - Future Cements

Geopolymer : Cement for low carbon economy

Sanjay Kumar and Rakesh Kumar

Geopolymer is emerging as future cement as it not only meets the critical properties of cement, but also falls under the
category of sustainability. The objective of this paper is to demonstrate the immense potential of geopolymer. It begins
with a short introduction defining geopolymer and mechanism of geopolymerisation. It is followed with an account of its
potential and commercial applicability. The flexibility of geopolymer in using waste and by-products has been discussed.
A comparison between properties of Portland and geopolymer cement has been made. The products developed at CSIR-
National Metallurgical Laboratory, Jamshedpur both at lab and pilot scale has been touched upon. Finally some of the
challenges associated with geopolymer have been highlighted.

Keywords: Geopolymer; low carbon; cement; fly ash; slag; characterization; properties.

1.0. Introduction 5 of Figure 1. It is produced at ambient or near ambient

Portland cement is not considered sustainable due to
energy intensive process and high CO2 generation. It
is estimated that production of 1 ton of cement clinker
requires 2.9 to 4.7 GJ energy and produces ~800 kg of
CO2 [1]. The European Cement Bureau in the technology
roadmap “The role of cement in the 2050 low carbon
economy” presented their vision for cement industry [2].
They suggested five ways to reduce carbon emission in
order to achieve sustainability as given in Figure 1 In
order to become sustainable, switching to alternate fuels
and substituting clinker with industrial wastes are some
of the technological options for cement industry. But
existing practices alone cannot reduce CO2 emissions
indefinitely and there is urgent need of a break-through
technology. Geopolymer is one such option which looks
very close to it and addresses the point no. 1, 2, 4 and
The Indian Concrete Journal, July 2014, Vol. 88, Issue 7, pp. 29-37
temperature (20-80°C), [3] generates 80% less CO2 than
ordinary Portland cement [3], conserve natural resources
by using waste and by-products and can be recycled as
aggregate after end of life.
The term geopolymer was coined nearly three decades
back by Davidovits for alumino-silicate polymers
formed in alkaline environment [3]. Geosynthesis or
geopolymerisation is the process of making geopolymers
at low temperature by chemical reactions between various
alumino-silicate oxides and silicates under highly alkaline
conditions, yielding polymeric Si–O–Al–O bonds [3,4] , as
described by the formula:
Mn [ – (Si – O2)z – Al – O ]n . wH2O ...(1)
(where M is an alkaline element, the symbol ‘–‘ indicate
presence of a bond, z is 1, 2 or 3, and n is degree of

The Indian Concrete Journal July 2014 29

TECHNICAL PAPER Special Issue - Future Cements

1 2 3 4 5
Carbon sequestration
Resource efficiency Energy efficiency Product efficiency Downstream
and reuse

Alternative fuels Electrical energy Carbon sequestration Low carbon concrete Smart buildings
efficiency and reuse & infrastructure
Raw material development
substitution Thermal energy Biological carbon
efficiency capture Recycling concrete
Clinker substitution

Novel cements Recarbonation

Transport efficiency Sustainable

Construction

Figure 1. Five routes to achieve sustainability

polymerization). The alumino-silicate mineral polymers

formed due to geosynthesis may have amorphous to
Aluminosilicate Source
semi-crystalline structure.
+
M(aq) H 2O
-
2.0. Mechanisms of OH (aq)
Dissolution

Geopolymerisation Aluminate & Silicate

Speciation
The general mechanism for the alkali activation of Equilibrium
H 2O
alumino-silicate materials was first proposed by
Glukhovsky in 1950s [5]. This model divides the process
into three Stages, destruction–coagulation, coagulation–
condensation, condensation–crystallization. After that a H 2O
Gelation
varieties of models have been proposed, but the simplified
Gel 1
reaction mechanism proposed by Duxton et al [6] is
the most widely used of geopolymerisation as given in
H 2O
Reorganization
Figure 2. The main reaction mechanism, which includes
dissolution, specific equilibrium, gelation, reorganization, Gel 2
polymerization and hardening, is presented linearly, but
these processes occur simultaneously and are largely H 2O Polymerixation
and Hardening
coupled.

The raw material and processing conditions leads to

wide variety of properties in geopolymers such as
high compressive strength, low shrinkage, fast or slow
Figure 2. Conceptual mechanism of geopolymerisation ( Duxton et
setting, acid resistance, fire resistance and low thermal
al., 2007

30 The Indian Concrete Journal July 2014

TECHNICAL PAPER Special Issue - Future Cements

conductivity. The characteristic of raw material which
affects the properties is its chemistry, glassy and crystalline
structure, reactivity and impurities. The ratio of SiO2 and
Al2O3 plays an important role in determining the type
and properties of geopolymer. The low Si:Al ratio (1,2,3)
results into a rigid 3D-Network, whereas a high Si:Al ratio
(>15) leads to polymeric character of geopolymer [3].
3.0. Immense Application and
Commercial Potential
To get the desired properties, the geopolymers
are processed in three different ways, (a) In-situ
geopolymerisation of alumino-silicate materials and
directly converting them to product, e.g. cement, tiles,
etc, (b) Preparation of geopolymer glue for binding
the aggregates, other materials, e.g. composites,
concrete, etc, and (c) Use of geopolymer as precursor
for high temperature application e.g. moulds, tools,
etc. By controlling the raw material characteristic and
optimizing the processing, the properties of geopolymer
can be tailored. Due to the flexibility of tailoring the
properties, geopolymers can be used in a wide spectrum
of applications. Main applications of geopolymers are
summarized in Table 1. The range of applications that are
possible is quite evident from Table 1.
4.0. Geopolymers in Wealth from
Waste Cycle
Conventionally metakaolin synthesized by
dehydroxylation of phase pure kaolin is used as main
raw material for geopolymers. However, thermal energy
required to convert kaolin to metakaolin by calcinations,
high water demand and low flowability have restricted the
usage of geopolymers to high value added applications.

Table 1. Applications of geopolymers

Area Applications Commercial production Reference

Civil engineering Low CO2, fast setting cement, precast concrete products and ready Ecrete by Zeobond, Australia 7-9
mixed concrete
banahCEM by BANAH, UK,
ROCLA concrete, Australia

Building materials Bricks, blocks, pavers, self glazed tiles, acoustic panels, pipes, Millikens, USA 10,11
HySSil, Australia
Zazil, India

Archeology Archeological monuments by geopolymerisation 12, 13

Repairing & restoration

Composite material Tooling for aeronautics 14, 15

Functional composite for structural ceramic application

Fire resistant material Fire and heat resistant fiber composite material Geopolymite and geopolytherm, 16-18
patented by Geopolymer Institute
Carbon fiber composite
Refractory application Refractory moulds for metal casting Mould for casting of Al/Li alloys in 19-21
liquid state, Pachieny patent
Use of geopolymer as adhesive refractory

Refractory castables

Utilization of waste Use of fly ash, blast furnace slag and tailings for geopolymer 22-26
products

Immobilization of Encapsulation of domestic, hazardous, radioactive and Duralith (at lab scale) 27, 28
toxic materials contaminated materials in a very impervious, high strength
material

Others Paints, Coatings, Adhesive 29, 30

The Indian Concrete Journal July 2014 31

TECHNICAL PAPER Special Issue - Future Cements

SiMn slag, construction and demolition waste, induction

furnace slag, tailings, etc.

5.0. Portland cement Vs geopolymer

Geopolymer cement is projected as potential replacement
of Portland cement. This is mainly based on the
properties and sustainability criteria. We have made a
comparison between the properties of Portland cement
and geopolymer in Table 2.

The uniqueness of Portland cement lies in its application

where solid powder cement is mixed with water and
used for continuous or pre-casting as per requirement. It
has the flexibility to adopt some variation in temperature,
Recently there has been a shift in trend to use waste and
moisture content and mixing. At this stage, geopolymer
by-products e.g fly ash, granulated blast furnace slag
technology is not so mature. Most of the products
(GBFS), tailings, red mud, etc. This shift in trend is visible
developed and produced are precast products. Although,
in Figure 3 which shows the increasing number of papers
geopolymer cement is sold by few companies, it comes
published on use of industrial waste in geopolymers (data
in two or three parts, one of feedstock, second a reactive
compiled from Science Direct). Fly ash based geopolymers,
material and third the alkaline activator. These mixtures
despite similarities in molecular and nano-structure,
are sensitive to various parameters and need training for
shows better durability and strength than metakaolin
proper use.
geopolymers, and thus becoming material of choice in civil
engineering applications. The other advantages include
6.0. Developments at CSIR-National
better dimension stability, flowability, cheap and easy
Metallurgical Laboratory
availability. The most commonly waste and by-products
which has been tried for synthesizing geopolymers are Geopolymer research at CSIR-National Metallurgical
GBFS, fly ash, steel slag, red mud, copper and zinc slag, Laboratory (CSIR-NML), Jamshedpur, India started

Table 2. Portland cement Vs Geopolymer

Properties Portland Cement Geopolymer Remarks

Physico-Mechanical Properties

Usually set faster than Portland cement, but depends on raw material
Setting time 30 to 300 min 10-60 min
reactivity and alkali concentration

33-53 MPa after 28 30-120 MPa after 7 Strength can be tailored by optimising raw material reactivity and
Compressive strength
days days alkali concentration

More durable than Geopolymer systems are alumino-silicate based system which are
Durability Moderate,
Portland cement resistant to acid attack

Environmental Impact

CO2 emission in geopolymer is during production of alkali hydroxide

CO2 emission 800-900 kg/ton 150-200 kg/ton
and silicate from carbonates

Embodied energy 4000-4400 MJ/ton 2200-2400 MJ/ton As it mostly uses waste and by-products with no embodied energy

Water requirement ~600 liters/ton ~450 liters/ton Geopolymer do not need curing with water unlike Portland cement

32 The Indian Concrete Journal July 2014

TECHNICAL PAPER
in the year 2000 with emphasis on waste materials,
most notably fly ash. The earlier research was directed
towards fundamental understanding of process, reaction
mechanism, microstructure development and structure-
properties relationship. This basic understanding has
led to the development of numbers of novel geopolymer
materials, e.g. (a) high strength geopolymer cement with
120 MPa strength; (b) self glazed geopolymer tiles from
fly ash at a temperature below 100oC; and (c) Geopolymer
pavement tiles having 20-40 MPa strength through
synergistic utilisation of fly ash, BF slag and other wastes.
Each of these products is unique in terms of process and
properties. The research and development activities of
CSIR-NML have been summarized in Figure 4 [31]. The
total activities have been classified into four subgroups as
following:
1. Process and product development using elevated
temperature processing: As reported in literatures
[3, 6], geopolymerisation reaction is optimum at
60-90°C. Using this information, various products
have been developed. The most exiting of them is
self glazed wall tiles. The motivation of this work
come from the information on the Djoser’s blue
Figure 4. Geopolymer research activities at a glance in CSIR-NML
Special Issue - Future Cements
Egyptian faience tiles, found in Djoser’s funerary
complex at Saqqarah (3. dynasty), which is believed
to underwent a self-glazing process during
firing in the range of 800- 850°C [32-35]. We have
achieved self glazing at temperature below 100°C
by customization of geopolymerisation reaction
through control of chemistry, reactivity and
processing conditions. Based on microstructural
and XRD studies it was interesting to know that
the dense microstructure on the surface of the
glazed tiles comprised of closely knitted grains
of mainly gismodine (a Na containing calcium
alumino-silicate mineral) in the glazed surface.
The tiles developed conform to the European
Nation (EN) specification for wall tiles. The other
products developed are mortar and concrete from
construction and demolition waste, and high
strength cement from fly ash.
2. Ambient temperature geopolymerisation:
Due to limitation of elevated temperature
geopolymerisation in large scale and onsite
application, a program on ambient temperature
geopolymerisation has been initiated. In order to
improve strength, the reactivity of raw material has
been altered by two approach, (a) addition more
reactive component, and (b) mechanical activation
of raw material. Geopolymer cement and concrete
has been developed using fly ash and granulated
blast furnace slag which achieve good mechanical
properties at ambient temperature (Figure 4).
Based on this understanding, paving blocks has
been developed which met IS 15658 specification.
Up-scaling of this process will be discussed in later
sections.
3. Preprocessing of raw material: Upto 120 MPa
compressive strength, which is perhaps the highest
reported, makes the developed geopolymer cements
distinct (Figure 5). The cement develops sufficient
strength within 24 h and ready for use. The strength
of the cements can be tailored through alteration in
fly ash reactivity by mechanical activation and/or
size classification. The superiority of mechanically
induced reactivity (attrition milled fly ash AMFA
and vibratory milled fly ash VMFA) over raw fly ash
The Indian Concrete Journal July 2014 33
TECHNICAL PAPER Special Issue - Future Cements

Impervious surface

Porous body

800
SiO2
700 Gismodine
CSH gel
600 Hydroki-sodalite
Intensity

500

400

300
Surface
200

100 Body

10 15 20 25 30 35 40 45 50 55

Figure 5. Mechanism of self glazing, the upper glazed surface and lower unglazed surface shows different microstructure
Compressive strength , MPa

30 120

25 100 Compressive strength , MPa

20 80

15 60

10 40

5 20
0
50% GBFS 25
H 25 35% GBFS VMFA
yd 20 Al 20
ra 25% GBFS ka AMFA
tio 15 li 15
n 15% GBFS co
tim 10 nc CFA
5% GBFS en 10
e, tra
da 5 RFA tio 5 RFA
ys n,
%

Figure 6. Variation in compressive strength of fly ash geopolymer in Figure 7. Variation in compressive strength of fly ash geopolymer
relation with GBFS content with respect to pre-processing

34 The Indian Concrete Journal July 2014

TECHNICAL PAPER
Table 3. Properties of paving block & its compliance with IS specification
Sl. No Property
Obligatory Requirement
1 Visual Inspection
2 Size tolerance, mm (L+W)
3 Water absorption, %
2
4 Compressive strength, N/mm
(RFA) and classified fly ash (CFA) can be attributed
to combined effect of particle breakage (surface
area) and other bulk and surface physicochemical
changes, vis-à-vis glass content induced reactivity
(CFA).
4. Hybrid geopolymer: This is the new research
direction which we started only 3 years back. The
target of this research was to develop products with
good compressive strength as well as good flexural
strength. Inorganic-organic hybrid geopolymer
has been developed which are lightweight, and
less brittle than conventional geopolymer with 3D
framework structure.
Translating science into technology
To study the commercial feasibility of geopolymer
products developed at lab scale, CSIR-NML has set up
the first geopolymer pilot plant in India with partial
Figure 8. Fully automatic geopolymer pilot plant at CSIR-NML
Special Issue - Future Cements
IS 15658 Specification Paving block from waste Remarks
Free from visual defect Free from visual defects Complies
±2 ±1 Complies
<7 <6 Complies
30 (80 mm thick) >35 (80 mm thick) Complies
funding from Fly Ash Unit, Department of Science and
Technology, Govt. of India. This is fully automatic plant
with 5 tons/shift capacity (Figure 8). The pilot plant has
been operated continuously and the process parameter to
produce paving blocks by geopolymerisation of fly ash
and GBFS has been optimized. In a further development,
CSIR-NML has developed the technology of paving blocks
jointly with Tata Steel, Jamshedpur. The raw material
used were steel slag, fly ash and GBFS combination. An
entrepreneur has been trained on the technology and he
produced 1200 tons of trial samples of paving blocks.
Table 3 shows the properties of paving blocks which
conform to IS 5658 specification.
These products were laid in different parts and monitored
continuously for 2 years. No deterioration in the product
properties has been observed. This technology has been
commercialized and further four more entrepreneur are
nurtured to produce this product using our technology.
In order to access the environmental impact of geopolymer
product, a life cycle analysis within the system boundary
of cradle to gate has been carried out using conventional
concrete as reference material. The various data which
has been analyzed were global warming potential,
energy cycle, acidification and toxicity potential, resource
conservation, material, energy and elemental balance.
The data on CO2 generation and energy consumption
has been given in Figure 9. It is clear from the graph that
geopolymer demonstrate superiority in terms of CO2
emission and energy consumption.
7.0. Challenges and issues
Although geopolymer is considered future cement, it is
premature to say that it will replace the OPC. There are
The Indian Concrete Journal July 2014 35
TECHNICAL PAPER
5000
1500
4000
Kg, CO 2 equivalent
Energy, MJ
1000
3000
500
2000
1000 0 of energy consumption, green house gas emission,
OPC based Geopolymer
Paving block Paving block
Figure 9. Life cycle analysis showing CO2 emission and embodied
energy content of conventional OPC based and geopolymer
concrete.
many issues and challenges which need to be addressed.
Some of it are technical and some non-technical. We have
listed down some of the major challenges as following:
a. Shifting from elevated temperature to ambient
temperature geopolymerisation: It is reported that
the geopolymerisation reaction and consequently
strength development is better if the reaction
carried out between 60-85ºC. However, this restricts
the use of geopolymer for large scale application
on site. Recent researches show that blending fly
ash with GBFS gives sufficient strength at ambient
temperature. This area needs more studies as there
is wide variation in ambient temperature with
season and geographic location change.
b. Efflorescence: In case of un-reacted alkali,
efflorescence has been observed on the surface of
the product. This was more prominent especially
during winter season when temperature was
<10◦C. This problem was solved by adding some
reactive material in composition and accelerating
the rate of reaction.
c. Development of standards: Geopolymer do not
have its own standard and is often judged on the
standard of products developed by other process,
which creates problem in marketing. There is urgent
36 The Indian Concrete Journal July 2014
Special Issue - Future Cements
need to develop standard for geopolymer process
and products. RILEM has formed a technical
committee to draw guidelines for alkali activated
material. That will be very useful in strengthening
the geopolymer activities.
Concluding remarks
Geopolymer can be considered as binder for low
carbon economy as it has immense potential in terms
resource conservation and above all excellent mechanical
properties. These are fast emerging materials of choice
for a range of building materials, fire resistance ceramics,
composites, matrix for immobilization of toxic wastes, and
many others. The global interest of scientific community
and technologist in these new generation materials stem
from the large possibility to tailor wide spectrum of
structure at or near ambient temperature for engineering
properties. At present, geopolymer technology is at the
nascent stage. Thus there is a strong need of collaboration
between research institutes and industry to address
various challenges to take it to maturity stage.
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Dr Sanjay Kumar holds a PhD in Ceramic Engineering and is Fellow, Indian Institute of Ceramics with
20 years of R&D Experience in the area of ceramics & waste utilization. He is Principal Scientist and
Group Leader, Recycling & Waste Utilization, CSIR-National Metallurgical Laboratory, Jamshedpur.
He has commercialised first geopolymer technology in India and having more than 100 publication with
700 citations, 15 patents, authored 2 book chapters, co-editor of two journals, and more than 30 invited
talk. He received Prestigious NMD Metallurgist of the Year Award 2013 given by Ministry of Steel,
Government of India (Environment Category), Viswakarma Award 2013 given by Construction Industry
Development Board, Planning Commission, Government of India. He worked at University of Santiago
de Compostella, Spain as Guest researcher under Research Excellence Fellowship. Currently he is leading
a comprehensive research program on fly ash under 12th five year plan and 4 international collaborative
project on geopolymer. He is also guiding 2 Ph.D, 3 M.Tech and 1 CV Raman Fellow from Africa and 1
RFTDC Fellow from Nepal on geopolymer related research.

Dr Rakesh Kumar holds a PhD in Metallurgical Engineering from Indian Institute of Technology, Kanpur.
He is Chief Scientist and Group Leader, Non-Ferrous Metallurgy Group, CSIR-National Metallurgical
Laboratory, Jamshedpur. His areas of interest are hydrometallurgy, Mechanochemistry and waste
utilization. He is having more than 60 publications with 600 citations, 8 patents and authored 2 book
chapters. He has received Prestigious NMD Metallurgist of the Year Award given by Ministry of Steel,
Govt of India (Environment Category), Altekar Award, Tamotia Award, etc.

The Indian Concrete Journal July 2014 37

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