Pozzolanicity of Calcined Clay

Anjan K Chatterjee

Abstract Out of the three major clay mineral groups, viz, kaolin, smectite and
palygorskite attapulgite, the cement science primarily focuses on the rst group to
be used on calcination as a pozzolanic admixture. The general understanding is that
the dehydroxylation of dehydrated kaolinite in the temperature range of 550 650 C
apparently yields an x-ray amorphous alumino-silicate phase which provides the
pozzolanic property to clay. There is not much of information on how the highly
crystalline kaolinite loses its long-range order in the lattice on account of dehydr-
oxylation. Little data are available on the effect of cation exchange capacity on
pozzolanicity. Further, in EN-197-1 the usability of a calcined clay as a pozzolana has
been linked with the presence of minimum 25 per cent reactive silica in it. The test
methods for determining the pozzolanic property of calcined clays are still in the
realm of arbitrariness. The present paper is a brief crystallo-chemical disquisition of
the above issues, based on the characterization of six different Indian clay samples.

1 Introduction

Although there are three distinctly different groups of clay materials, viz., kaolin,
smectite and palygorskite of industrial signicance, the construction industry in
general and the cement industry in particular mostly make use of kaolin in raw and
processed forms. Specically for use as a supplementary cementitious material in
blended cement or concrete, thermal treatment of kaolinitic clays to a temperature
beyond dehydroxylation is taken recourse to in order to activate their pozzolanic
properties. The reactivities of dehydroxylated kaolinite with lime as determined
through a standard test procedure is taken as its pozzolanic capacity. Through actual

A.K. Chatterjee (&)

Conmat Technologies Private Limited, Kolkata, India
e-mail: anjan.k.chatterjee@gmail.com

RILEM 2015 83
K. Scrivener and A. Favier (eds.), Calcined Clays for Sustainable Concrete,
RILEM Bookseries 10, DOI 10.1007/978-94-017-9939-3_11
84 A.K. Chatterjee

practice it has been established beyond doubt that the dehydroxylated kaolin (also
called metakaolin) is x-ray amorphous in nature and releases alumina and silica in
the course of cement hydration to form calcium alumino-silicate hydrate phases that
enhance the strength and durability of concrete.
Similar reactions and effects are not observed with smectite and palygorskite
groups of clay minerals upon dehydroxylation. It is also known that these groups of
clay minerals often occur as associate minerals in kaolinitic clay, causing alteration
in its pozzolanic behaviour and capacity. Although the published literature on clay
minerals is profuse, it is not very clear how crystalline kaolinitic phase loses its
crystallinity on account of dehydroxylation and make the anhydrous alumino-sili-
cate phase soluble and reactive. The dissimilar behaviour of the other two major
clay mineral groups under similar circumstances also awaits an explanation.
Another issue that has cropped up in the context of EN-197-1 is the validity of
specifying the content of minimum 25 per cent reactive silica in a calcined clay to
qualify as a pozzolana.
This paper is intended to address the above issues in a concise manner based on
characterization features of some diverse clay minerals.

2 Distinctive Features of the Major Clay Mineral Groups

It is well known that the clay minerals are part of a larger family of phyllosilicates
and are characterized by interlinked tetrahedral and octahedral sheets. The structural
conguration of clay minerals has been dealt with in fair detail by Grim [1, 2],
Brindley and Brown [3], Velde [4] and others [5], a summary of which is presented
in Table 1.
As a result of constitutional diversity, the technical assessment of clays is rather
complex. In broad terms the property controlling factors are the following:
clay mineral species present
occurrence of non-clay minerals
presence of organic substances
exchangeable ions
particle characteristics (shape, size, orientation, etc.)
structural assembly of 1 : 1 or 2 : 1 linkage of tetrahedral and octahedral sheets
as well as neutralization of excess layer charge by various interlayer materials.
Calcination of clays and their thermochemical reactivity have been dealt with in
[69].
Table 1 Structure and properties of the major clay mineral groups
Structural Major mineral Broad composition Structural features Cation
grouping phase exchange
capacity
meq/100 g
2-layer Kaolinite (OH)8Si4Al4O10SiO246.54 % 1:1 layer type (001) = 7.21 A 315
kaolin group Al2O3 39.50 % B = 8.99 A
Pozzolanicity of Calcined Clay

H2O 13.96 % Flaky habit

3-layer Montmorillonite (OH2)4Si8 Al4O20.nH2O 2:1 layer. 80150
smectite (Expanding Composition without interlayer material : Equidimensional extremely thin flakes
group lattice)
SiO2 66.7 %
Al2O3 28.3 %
H2O 5.0 %
Some substitution of Si by Al in tetrahydral layer
and of Al in octahedral layer by Mg, Fe, Zn, Ni, Li,
etc. Lattice always unbalanced
Illite (Non- Muscovite like dioctahedral (OH)4K2 (Si6Al2) Structural characterization same as micas, 1040
expanding Al4O20 Biotite type is trioctahedral with 2 : 1 layer type. Small poorly dened flake
lattice) incorporation of Mg and Fe. Illites differ from mica commonly grouped in irregular aggregates
in having less replacement of Al for Si, less K and
less randomness of silicate layers
Chain- Palygorskite Composition of the balanced ideal cell of Attapulgite 2:1 inverted ribbons. Generally seem as 2050
structure Attapulgite - (OH2)4(OH)2 Mg5Si8O.4H2O Sepiolite and bundles of lath-shape units
palygorskite Sepiolite palygorskite show variations in the composition of
group Al, Mg and Si
85
86 A.K. Chatterjee

3 Characterization of Some Clay Samples and Their

Pozzolanic Capacity

In the backdrop of what has been discussed above six Indian clay samples were
randomly chosen and characterized. The oxide composition of these clays is given
in Table 2. The corresponding phase analyses of the same samples are also shown
in the same table.
The XRD patterns showed that on calcining of samples 1, 2 and 3 in a muffle
furnace at 900 C for 30 min the kaolinite phase could be totally dehydroxylated and
made x-ray amorphous, while for sample No. 4 having goethite as an associate phase
and sample No. 5, which was a mixture of kaolinite and illite, the total breakdown of
the clay minerals could not be achieved. So far as the montmorillonitic clay is
concerned, this phase was almost broken down on calcination at 900 C but the
hematite phase appeared to have recrystallized.
The above six samples were also subjected to thermal analysis and the weight
loss values for all the six samples against temperature are summarised in Table 3.
In further characterization of the clay samples the Reactive Silica contents and
their Cation Exchange Capacities were determined. In parallel the Lime reactivities
of the calcined clays were also tested [10]. These results are presented in Table 4.
Data presented in Table 4 do not show any trend of conformity of the kaolonite
contents, CEC values, presence of reactive silica and lime reactivity results. Thus,
adoption of any one indirect index to evaluate the pozzolanic capability of a clay on
calcination still remains quite arbitrary. Cara et al., based on their evaluation work
of calcined kaolinitic clay of an Italian mine, came to the conclusion that the only

Table 2 Chemical and mineral composition of the clay samples

Oxides [1] [2] [3] [4] [5] [6]
LOI 13.72 13.48 11.06 7.76 9.96 9.63
SiO2 46.02 45.95 60.41 53.60 56.98 52.55
Al2O3 35.90 36.05 26.24 16.68 27.10 24.01
Fe2O3 1.18 1.95 0.62 12.01 2.07 8.05
CaO 0.33 0.44 0.96 0.78 0.21 0.30
MgO 0.16 0.16 0.10 4.68 0.06 0.40
Na2O 0.07 0.08 0.03 1.20 0.03 2.25
K2O 0.02 0.10 0.15 0.69 1.26 0.10
TiO2 1.86 1.68 0.22 2.02 2.21 2.20
Total 99.28 99.89 99.79 99.42 99.88 99.51
Phase analysis
Minerals Kaolinite Kaolinite Kaolinite Kaolinite Quartz Montmori-
present Anatase Quartz Quartz Quartz Kaolinite llonite
Anatase Muscovite Anatase Illite Hematite
Goethite Anatase Quartz
Hematite Cristobalite
Anorthoclase Anatase
Pozzolanicity of Calcined Clay 87

Table 3 Weight losses of the clay samples as obtained from TGA curves
Sample No. Temperature range, 0 C Wt. loss % Remarks
1 Up to 350 1.20 Moisture loss
350 650 13.34 Dehydroxylation of kaolinite
2 Up to 350 1.40 Moisture loss
350 650 12.14 Dehydroxylation of kaolinite
3 Up to 250 0.42 Moisture loss
250 750 10.05 Dehydroxylation of kaolinite
4 Up to 200 8.65 Moisture loss
200 350 1.03 Breakdown of goethite
350 750 4.36 Dehydroxylation of kaolinite
5 Up to 400 1.30 Moisture loss from illite
400 550 5.70 Incomplete dehydroxylation of kaolinite
500 1000 4.00 Prolonged breakdown of clay minerals
6 Up to 100 12.00 Moisture loss
100 700 7.00 Dehydroxylation of kaolinite

Table 4 Indirect indices of pozzolanic capacity of the clay sample

Sample Major clay minerals Cation Exchange Reactive Lime Reactivity,
No. Capacity meq/100 g Silica % N/mn2
1 90 % kaolinite 3.5 36.2 9.2 at 900 C
2 80 % kaolinite 3.1 31.5 8.6 at 900 C
3 70 % kaolinite 12.8 27.4 7.6 at 900 C
4 40 % kaolinite 19.4 18.7 3.9 at 900 C
5 50 % kaolinite + 14 % 13.2 27.6 12.4 at 600 C
illite
6 6 % kaolinite + 80 % 86.5 49.8 5.1 at 700 C
montmorillonite

investigation that could shed light upon the pozzolanic properties are those based
on the determination of the effective calcium hydroxide consumption [11]. Their
data, however, indicated that the total consumption of lime by the calcined kao-
linitic clays in pastes took 180 days for most of the samples and the residual values
of lime at all prior ages were quite random and erratic. A fairly similar study carried
out by Fabbri et al. [12] also indicated that the pozzolanic activity of metakaolin
should be evaluated after at least seven days of reaction with calcium hydroxide and
the authors suggested that an average value from the 7, 14 and 28 days of curing
might be used to indirectly evaluate the pozzolanic potential of a given clay sample.
The thermal analysis of kaolinite has been extensively studied by Chakraborty
[13]. The broad ndings were that a poorly crystallized kaolinite showed a
comparatively lower temperature endothermic and exothermic peaks than the
88 A.K. Chatterjee

Table 5 Reactive silica contents of samples 5 and 6

Constituents Sample no. 5 Sample no. 6
200 C 700 C 900 C 200 C 600 C 900 C
LOI (%) 9.53 1.68 0.3 9.63 2.35 0.24
Total SiO2 (%) 57.7 61.93 63.39 52.55 55.68 57.22
Reactive SiO2 (%) 27.58 38.59 34.19 49.81 44.80 34.19
Reactive SiO2 as percentage of total 48 62 54 94 80 60
SiO2 on LFB

well-crystallized variety but its ultimate effect on the pozzolanic potential has not
been dealt with. It appears that the pozzolanic potential of a dehydroxylated kao-
linite depends on the completeness of the dehydroxylation process, the specic
surface area generated, the absence of recrystallization and agglomeration and the
presence of associated clay and non-clay minerals. The signicant presence of illite
and predominance of montmorillonite in the clay composition alter the dehydr-
oxylation behaviour of calcined clays and their resultant pozzolanic potential.
The factors influencing the acid/alkali solubility of the x-ray amorphous
alumino-silicate phase are still not very evident. The content of reactive silica,
which is a fairly reliable index of the pozzolanic potential of glassy fly ash, does not
seem to be an effective indicator of pozzolanic capacity of metakaolinitic materials.
In the sample Nos. 5 and 6 the reactive silica contents at different temperatures of
calcination were found to be quite high (Table 5). It is interesting to note from
Table 5 that the reactive silica percentages in Sample Nos. 5 and 6 were apparently
high in uncalcined state but on calcination Sample No. 5 showed a maximum at
700 C, while sample No. 6 showed progressive reduction with temperature.
Further, the trend of reactive silica contents for both the samples did not conform
with the Lime Reactivity values.
Finally, the CEC values (see Table 4) seem to behave more like a tool to identify
the clay minerals present in an argillaceous substance, based on their structural
congurations. The layers in kaolinite are held together by fairly weak bonds,
whereas there is strong bonding in illite and montmorillonite because of the pres-
ence of positively charged metal ions potassium in the case of illite and sodium in
the case of montmorillonite. These crystallochemical differences are reflected in the
CEC values.

4 Conclusions

Calcined clay is an important pozzolanic substance in making blended cement and

concrete. Since all clays do not display comparable pozzolanic potential, a more
in-depth study of the crystal chemistry of the clay minerals is necessary for precise
prognosis of their pozzolanic behaviour. In the present study involving three clay
samples of varying kaolinite content with some non-clay minerals, one clay sample
Pozzolanicity of Calcined Clay 89

with associated goethite and hematite, another clay having a mix of kaolinite and
illite and the sixth clay sample which is predominantly montmorillonite in com-
position, the following observations could be made :
i. The rst three kaolinite clays with kaolinite contents ranging from 70 to 90 per
cent showed an increasing trend of lime reactivity and reactive silica contents
but CEC values do not conform to this trend.
ii. The other three clay samples containing goethite, illite and montmorillonite
show signicantly different values of lime reactivity, reactive silica and CEC.
iii. The CEC results seem to provide good indication of clay mineral types and can
perhaps be developed into an indirect measure of pozzolanicity, the work on
which is progressing in the authors laboratory.
iv. The reactive silica content did not appear to be a reliable indicator as anomalous
values were obtained, particularly for impure kaolin and smectite groups of
clays.

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