Natural Zeolites, an option as a partial replacement for

Ordinary Portland Cement, a Review

Cristian A. Flrez a , Jorge Ivn Tobnb , Oscar J. Restrepoc.
a,b,c

Departamento de Materiales y Minerales, Grupo del Cemento y Materiales de Construccin,

Universidad Nacional de Colombia.
ARTICLE INFO

ABSTRACT

Article history:

Natural zeolites are hydrated aluminum silicate minerals with a

tetrahedral crystalline structure which make them different from other
supplementary cementitious materials like fly ash, silica fume among
others. Some advantageous properties of zeolites are their regular
(honeycomb) structure, large high surface area, large inner specific
surface area, uniform size pores, good strong adsorption capacity,
among others. Heulandite and clinoptilolite both monoclinical zeolite
minerals are the most abundant zeolites types in nature. Zeolites are
pozzolans that are composed by a high reactive SiO 2 and Al2O3 and
are able to combine with portlandite (Ca(OH)2), a by-product of
cement hydration. As supplementary cementitious material, zeolite
enhances the durability, reduce the heat of hydration, increase the
resistance to sulfate attack and reduce the energy cost per cement
unit.

Working on it

Keywords:
Natural Zeolite
Clinoptilolite
Pozzolan
Cement

Content
1.

Introduction................................................................................................................................. 2

2.

Objective.................................................................................................................................... 3

3.

Authors and Materials................................................................................................................. 3

4.

Results and Discussion.............................................................................................................. 4

5.

Conclusions................................................................................................................................ 7

6.

Acknowledgments...................................................................................................................... 7

7.

References................................................................................................................................. 7

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1. Introduction
Since ancient times, zeolites have been
generally used as an additive in constructions
around the world.
It is widely known that pozzolans can improve
some properties like give a durability
increase, decrease the heat of hydration,
enhance the resistance to sulfate attack and
reduce the energy cost per cement unit
(Kocak, Tasci, & Kaya, 2013).
Nowadays, more than 50 natural and 150
synthetic zeolite minerals are known and
used in different industries (Ahmadi &
Shekarchi, 2010). Natural zeolites are
hydrated aluminosilicate minerals with a
tetrahedral crystalline structure, which make
them different from other supplementary
cementitious materials.
The most abundant and most common type
of natural zeolite minerals on earth are
clinoptilolite, heulandite, analcime, chabazite,
and mordenite. However in this review we are
just going to talk about heulandite and
clinoptilolite mostly.

three different types of channel, A, B, and C

(Wise & Santa, 2005).
It is generally known that natural zeolites are
an especial type of natural pozzolan which
has been recently applied in various cement
and concrete manufacturing plants around
europe and some other countries like iran,
cuba, china, inter alia.
These natural zeolites has a substantial
pozzolanic activity despite their noticeable
crystalline structure.
Pozzolanic activity of natural zeolites has
been generally associated to dissolution of
these zeolitic crystals under the attack of OHions available in hydrating cementitious
system
which
are
composed
by
threedimensional microporous honeycomb
structures
that offers large internal and
external surfaces.
The large quantity of reactive SiO 2 and Al2O3
in zeolite chemically combines with the
calcium hydroxide produced by the hydration
of cement to form additional CSH gel and
aluminates, resulting in the improvement of
microstructure of hardened cement (Ahmadi
& Shekarchi, 2010).
Replacement of natural zeolites as a
supplementary cementitious materials can
improve some mechanical properties of
cement and concrete composites but also
increases water demand due to zeolites
porosity. Despite of their several advantages,
natural zeolites has not been researched as
deep as other pozzolans.
According to Scopus, using keywords as
zeolites and natural pozzolans, Fig. 2 show
us the publications number per year, which
confirms that these zeolites has not been
extensively researched.

Fig. 1 Honeycomb framework of heulandite

and clinoptilolite, composed by impermeable
sheets (i.s.) which are cross-linked, forming

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Fig. 2 Research articles published from 1951 to 2016.

2. Objective
Study, compare and analyze different results
that can prove that natural zeolites can be
used as a supplementary cementitious
material.

3. Authors and Materials

Materials used by (Ahmadi & Shekarchi,
2010) were a ASTM Type II Portland cement,
natural zeolites (Clinoptilolite type) from Iran
at different percentage concentrations (5%,
10%, 15%, 20%), silica fume with (5%, 10%,
12.5%) percentage concentrations and
Naphthalene superplasticizer (40% solid)
when they worked with concrete.
About mortars tests they worked with the
same natural zeolites percentages but
instead silica fume they used fly ash at (10%,
20%, 30%, 40%) percentage concentrations.
The authors aim was to evaluate different
effects of natural zeolites on concrete
properties.

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According to (Perraki, Kontori, Tsivilis, &

Kakali, 2010), they monitored properties of
cement replaced with natural zeolites
(heulandite type-II) from Greece at 10% and
20 % working with Portland Cement (CEM I
42.5 N and CEM I 52.5 N) up to one year
making their tests on mortars only.
Turquish natural zeolites clinoptilolite type,
replacing Portland cement (CEM I 42.5 R)
with 5%, 10%, 15%, 20% and 30% by weight
were the materials used by (Bilim, 2011) for
his tests to evaluate the effect of this natural
pozzolan on mortars.
(Kocak et al., 2013) worked with natural
zeolites from turkey to determine their effect
and test some properties on pastes and
mortars, replacing CEM II 42.5 R portland
cement with Clinoptilolite at 5%, 10%, 15%,
20% by weight.
Researchers from Lithuania (Nagrockiene &
Girskas, 2016) used a replacement of
Clinoptilolite natural zeolite type at 2.5%, 5%,
7.5%, 10%, for CEM I 42.5 R cement in order
to analize concretes using Polycarboxylic
resin-based superplasticizers (0.2 2.5%).

Table. 1 Different types of cement and natural zeolites at different concentrations.

Fig. 3 Comparison between SF and NZ pozzolanic reactivity (Ahmadi & Shekarchi, 2010).

4. Results and Discussion

(Ahmadi & Shekarchi, 2010) Fig. 3
established that pozzolanic reactivity of silica
fume (SF) pastes are better than natural
zeolites, because at 14 days the silica fume
react 100% while the natural zeolite (NZ)
takes 28 days to react with the total amount
of Ca(OH)2. All the zeolite replacements
obtain higher compressive strengths in
concrete than control mixtures, however the
best option for zeolites is the one with a
replacement of 15% due to it has similar
results to silica fume in 10% and 12.5%.
About water absorption (concrete) and mortar
bars expansion due to ASR, all the natural
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zeolites mixes show lower values than control

mixture.
Results obtained by (Perraki et al., 2010) in
compressive strengths were lower than
control mixes except at 28 and 90 curing
days with Portland cement CEM I 42.5 N +
10% zeolites, Portland cement CEM I 52.5
N + 10% zeolites and Portland cement CEM
I 52.5 N + 20% zeolites.
Compressive and flexural strengths since 7 to
90 curing days for all mortars containing
zeolites at 5%, 10%, 15%, 20%, 30%, were
higher than reference mix and the relation
between water adsorption and porosity was
lineal according to (Bilim, 2011).

According to (Kocak et al., 2013)

compressive and flexural strengths in mortars
were lower than control mix, their setting time
does not have significant changes for all
zeolites additions.

Fig. 5 Concrete adsorption increasing natural

zeolites concentrations. (Nagrockiene &
Girskas, 2016)

Fig. 4 Concrete Ultrasonic velocity at 7 and

28 curing ages. (Nagrockiene & Girskas,
2016)
(Nagrockiene & Girskas, 2016) reported that
compressive strength (concrete) after 7 and
28 days of curing were significantly high for
all natural zeolites additive content. Besides,
he also measured the concrete ultrasonic
pulse velocity and its water adsorption. Fig.
4, Fig. 5.

(Bilim, 2011) also reported how these flexural

and compressive strengths change, after
expose the mixes to high temperatures and
freezethaw tests. Fig. 6, Fig. 7.
Comparing mortars compressive strengths
results between (Kocak et al., 2013) and
(Bilim, 2011) we can see in Fig. 8 that they
obtain very
different results as they
increased the natural zeolite (Clinoptilolite)
replacements.

Fig. 6 Decreasing compressive strengths at high temperatures. (Bilim, 2011)

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Fig. 7 Decreasing flexural strengths at high temperatures. (Bilim, 2011).

Fig. 8 Natural zeolites blended with different cement types. (Kocak et al., 2013) vs (Bilim, 2011).
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5. Conclusions
Zeolite type (Clinoptilolite - Heulandite) could
affect or improve blended cement properties,
giving higher or lower compressive and
flexural strengths than control mixes.
Natural zeolites can improve blended cement
properties like pozzolanic reactivity and get
higher compressive strengths (mortars and
concretes) than control mixes.
Natural zeolites on mortars and concrete
properties will change according to his
chemical composition.
Depending on zeolites porosity his water
adsortion will increase or do not.

6. Acknowledgments
Special thanks to Cement and Construction
Materials for their amazing support.

7. References
Ahmadi, B., & Shekarchi, M. (2010). Use of
natural zeolite as a supplementary
cementitious material. Cement and
Concrete Composites. Elsevier Ltd.
http://doi.org/10.1016/j.cemconcomp.20
09.10.006
Bilim, C. (2011). Properties of cement mortars
containing
clinoptilolite
as
a
supplementary cementitious material.
Construction and Building Materials.
Elsevier
Ltd.
http://doi.org/10.1016/j.conbuildmat.201
1.02.006
Kocak, Y., Tasci, E., & Kaya, U. (2013). The
effect of using natural zeolite on the
properties and hydration characteristics
of blended cements. Construction and
Building
Materials.
Elsevier
Ltd.
http://doi.org/10.1016/j.conbuildmat.201
3.05.033
Nagrockiene, D., & Girskas, G. (2016).
Research into the properties of concrete
modified with natural zeolite addition.
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Construction & Building Materials.

Elsevier
Ltd.
http://doi.org/10.1016/j.conbuildmat.201
6.03.133
Perraki, T., Kontori, E., Tsivilis, S., & Kakali,
G. (2010). The effect of zeolite on the
properties and hydration of blended
cements.
Cement
and
Concrete
Composites.
http://doi.org/10.1016/j.cemconcomp.20
09.10.004
Wise, W. S., & Santa, C. (2005). Structure of
Zeolites. Encyclopedia of Geology.

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