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A Review on Heat Released in early Geopolymerization by Calorimetric Study

Article  in  Materials Science Forum · August 2019

DOI: 10.4028/www.scientific.net/MSF.967.236

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Materials Science Forum Submitted: 2018-10-17
ISSN: 1662-9752, Vol. 967, pp 236-240 Revised: 2019-01-30
doi:10.4028/www.scientific.net/MSF.967.236 Accepted: 2019-05-01
© 2019 Trans Tech Publications Ltd, Switzerland Online: 2019-08-16

A Review on Heat Released in Early Geopolymerization by Calorimetric

Study
ROSNITA Mohamed1,2,a, RAFIZA Abd Razak1,2,b,
MOHD Mustafa Al Bakri Abdullah1,2,c
1
Center of Excellence Geopolymer and Green Technology (CEGeoGTech), School of Materials
Engineering, University Malaysia Perlis (UniMAP), P.O Box 77, d/a Pejabat Pos Besar, 01000
Kangar, Perlis, Malaysia
2
Faculty of Engineering Technology, Universiti Malaysia Perlis (UniMAP), P.O. Box 77, D/A
PejabatPosBesar, Kangar, Perlis 01000, Malaysia
a
rosnitamohamed21@gmail.com, brafizarazak@unimap.edu.my,
c
mustafa_albakri@unimap.edu.my

Keywords: Heat of hydration, geopolymer, metakaolin, fly ash, heat released, calorimetry

Abstract. An exothermic chemical reaction between cement and water or is called as hydration of
cement produced heat in which gives significance impact to the cement or concrete produced. This
hydration of cement is similar to geopolymerization as in geopolymerization, heat is liberated when
any pozzolanic material mixes with alkaline solution. Heat released for both hydration of cement and
geopolymerization can be measured in a form of calorimetric data. This paper reviews on the use of
heat released information for a better understanding on the reaction kinetics of geopolymerization
and correlating the heat released with several factors including concentration of alkaline solution,
mixing designation and curing temperature.

Introduction
Hydration of Portland cement generates heat and it is called heat of hydration. Heat of hydration
measurements is crucial in assessing temperature rise during the hydration process of Portland cement
[1]. Temperature rise occurs due to the exothermic nature of the interaction of anhydrous cement with
water. This temperature rise is crucial to be taken care of and if the temperature rise is significantly
high and undergoes non-uniform or rapid cooling this will lead to cracking to the cement paste before
or after it cools to the surrounding temperature. Therefore it is crucial to determine the heat of
hydration liberated.
The exothermic reaction of hydration of cement is similar to the exothermic reaction of
geopolymerization. Geopolymerization is a reaction between any pozzolanic material with alkaline
solution such as sodium hydroxide or sodium silicate. Therefore, heat released in both of the reactions
can be determined by same common method that has been used since 1900s which is calorimetry.
The calorimetry test has been used by Schutter [2] as a general hydration model for Portland cement.
Isothermal conduction calorimeter has become a powerful technique for determination of heat
released as it provides a real-time information [3] .A calorimetric technique using differential
scanning calorimeter, DSC for heat released study was also has been reported by Rahier et al [4].
The heat evolution data enables us to determine the optimum ratio suitable for geopolymerization
as it provides peaks for steps that occurs in geopolymerization [3,[5]. The total heat released also can
be determined based on the calorimetric data and using some models such as Knudsen model [6] and
based on the heat released information too, the apparent activation energy and degree of reaction can
be predicted in which lead to a better understanding of reaction kinetics of early geopolymerization.
Thus, this paper reviews on the heat released on early geopolymerization of different pozzolanic
material (fly ash and metakaolin) by focussing on the calorimetric data obtained.

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 Materials Science Forum Vol. 967 237

Calorimetric Study
Heat released in geopolymerization and hydration of Portland cement can be determined by using
calorimetric test. This method is one of a powerful technique for thermal analysis in geopolymer as
it provides a real-time information. Both raw material or cement and alkaline solution or water can
be mixed internally or externally for this technique. Two common instruments that is useful in
determining the heat released are isothermal conduction calorimeter, ICC and differential scanning
calorimeter, DSC. Differential scanning calorimeter, DSC measures the temperature and heat flow
(energy changes) that occur in a sample when it is heated, cooled, or held isothermally at constant
temperature. This is similar to ICC but commonly, ICC is preferable as the reaction usually takes
place internally. It gives key information regarding initial reaction heat change DSC method cannot
offer [4].

Heat Released of Early Geopolymerization for Metakaolin

Metakaolin is one of pozzolanic material that is suitable to be used in geopolymerization.
Metakaolin is produced by calcination of kaolinitic clay at temperature of between 650 °C and
800 °C depending on the purity and crystallinity of the precursor clays [7]. Heat evolution of early
geopolymerization of metakaolin has been reported by Zhang et al.,[3] in which focusing on the effect
of alkaline activating solution in geopolymerization. The heat evolved was monitored by using
isothermal conduction calorimetry for 72 hour with variation in alkaline solution concentration (only
sodium hydroxide was used as alkaline activator).
The peaks observed in heat evolution represented the proposed step that occurred in early
geopolymerization in which can be seen and summarized in Figure1. In Figure 1, from the variation
of amplitude in Peak I, it can be concluded that the maximum heat released increases as increasing in
NaOH concentration and temperature meanwhile for Peak II or a similar peak as ‘induction peak’ in
hydration of cement noted that the maximum heat released only increase until concentration of NaOH
was 10M and became decreasing when the concentration was increased to 12M. This shows that there
is an optimum alkalinity suitable for geopolymerization of metakaolin using NaOH. High
concentration of Na+ ions may be beneficial to dissolve aluminosilicate but undesirable to
polymerization [5]. Meanwhile, a third exothermic peak only can be observed at higher temperature
, which is attributed to the further reorganization of the solid structures into a more stable (although
not necessarily notably more crystalline) state [8].
A schematic diagram in Figure 2 summarised on the steps in geopolymerization of metakaolin.
Stage I is a dissolution stage of geopolymerization in which the aluminosilicates breaks into its
monomers of Si and Al. Stage II represents the polymerization and condensation of the monomers
meanwhile stage III shows a reorganization of polymers in which is a slow reaction. Part 2 of this
study by Zhang et al. [9] also gave a same trend of results even using different activating solution
(sodium silicate was used in part 2) and the thermochemical parameters were briefly described also
in part 2. As the reaction extent was calculated for both of the parts and enthalpy were calculated with
the help of characterization by Fourier Transform Infrared Spectroscopy (FT-IR) and X-Ray
Diffractometry (XRD) analysis, Zhang et al. concluded that the ratio of Na/Al influenced significantly
compared to Si/Al ratio. An optimum condition required such as solid/liquid ratio, reaction
temperature and concentration of alkaline activating solution also has been proven based on the
amplitude peaks of calorimetric data. As such these conditions could affect the heat released during
geopolymerization and compressive strength of geopolymer, both of heat released and compressive
strength may be correlated with each other.
238 Green Materials and Technology

Figure 1: Effects of NaOH concentration on heat evolution rate of MK geopolymerization at

(a) 20 ◦C, (b) 25 ◦C, (c) 30 ◦C, (d) 35 ◦C and (e) 40 ◦C (Zhang et al.,2012).
 Materials Science Forum Vol. 967 239

Figure 2: Schematic of the kinetics of geopolymer synthesis by NaOH activation of MK, as

determined by isothermal calorimetry (Zhang et al., 2012).

Heat Released of Early Geopolymerization for Fly Ash

There is an increasing demand for research of fly ash from the points of environmental pollution
prevention and by-product recycling as fly ash is a part of by-product produced by power plant [6].
Numerous studies have been conducted on mixing fly ash with other material such as adding a small
amount or ratio of fly ash in Portland cement or combining it with slag but only few studies have
been conducted focussing on the fly ash geopolymerization itself due to its complexity such as slow
reactivity, heteregenous nature of the fly ash and the non-uniform and multiple reaction paths in
reaction mechanism [6].
The reaction kinetics of fly ash(class F) geopolymerization has been reported by Nath et al.[6] by
using the calorimetric data of heat evolution obtained with various in reaction
temperature(temperature selection was selected based on literature studies on curing temperature of
fly ash geopolymer). In conclusion of the study, the reaction mechanism in early fly ash
geopolymerization was controlled by nucleation and growth kinetics in which relevant to its slow
reactivity. A higher activation energy required to initiate the early geopolymerization compared to
Portland cement and slag (particularly GBFS) due to its chemical composition therefore making it
more sensitive to temperature. Therefore, the small addition of fly ash in Portland cement acts as a
natural retarder for reducing heat liberated in hydration in which can lead to temperature rise of
cement.

Figure 3: (a) ICC plot of fly ash alkali activation at different temperatures (a-34, b-39, c-45, d-52,
and e-60℃). (b) Heat evolution of reaction up to 29.6 h time (Nath et al.,2016).
 240 Green Materials and Technology

Summary
Heat evolution in early geopolymerization can be concluded as crucial in controlling the
mechanism of early geopolymerization. It is proven to be affected by certain factors such as
concentration of activating solution and reaction temperature. Different pozzolanic materials also
produced different amount of heat released as each of pozzolanic materials have different chemical
composition. For instance, fly ash class F has a very slow reactivity due to its minimal amount of
Calcium, Ca. As previous studies focussing on heat released in geopolymerization for the whole
proposed steps in geopolymerization, a further study on correlating the heat released during
geopolymerization to the mechanical testing will be useful to give a better understanding in
geopolymer. Both of fly ash and metakaolin have been widely studied for its mechanical properties
but the chemical insight of the reaction mechanism using these materials remain to be discovered.

Acknowledgement
We would like to appreciate Centre of Excellence Geopolymer and Green Technology
(CeGeoGTech), School of Material Engineering, Universiti Malaysia Perlis.

References
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