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 Chapter 8

Characterizations and Industrial Applications for

Cement and Concrete Incorporated Natural Zeolite

Iván Ayoseth Chulines Domínguez,

Chulines Domínguez,
Youness Abdellaoui,
Youness Abdellaoui, Mohamed Abatal
Mohamed Abatal and
and
Cristóbal Patiño-Carachure
Cristóbal Patiño-Carachure
Additional information
Additional information is
is available
available at
at the
the end
end of
of the
the chapter
chapter

http://dx.doi.org/10.5772/intechopen.74953

Abstract

Zeolites have been widely used in various industries, leading to a high commercial value;
this is mainly due to the wide diversity of naturally occurring species and the ability to
synthesize new types. In the cement and concrete industry, natural zeolite is a popular nat-
ural pozzolanic material in some regions of the world owing to their economic, environ-
mental, and technical advantages, among others, used pozzolanic materials. Many works
have reported the use of natural zeolite as substituent material for cement in mortar and
concrete. Generally, the use of natural zeolite can overcome environmental and economic
problems associated with the use of high quantity of cement; furthermore, it is shown
a strength enhancement and durability improvement properties of cement and concrete
composites. In this context, this chapter strives to review the application of natural zeolite
as pozzolan in cement and concrete composites, its characteristic, its proper incorporation,
and each of the influencing parameters. In addition, the elaboration methods, textural and
mechanical characterization, and applications of these composites will be treated.

Keywords: cement substitution, concrete, hydration, pozzolanic material, natural

zeolite

1. Introduction

The number of zeolites is constantly increasing; currently, the commission of structures of

the International Zeolite Association (IZA) recognizes 232 unique structures that have been
approved and have been assigned three letters of code [1]. The chemistry of zeolite has been

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative
Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
distribution, and reproduction in any medium, provided the original work is properly cited.
136 Zeolites and Their Applications

a subject of significant interest due to the ion exchange properties of zeolite, crystallinity,
thermal stability, and well-defined molecular size closed structures [2]. The code ASTM-618
(American Society for Testing Materials) defines pozzolans as siliceous or aluminum-siliceous
materials, which by themselves have little to no cementing value, but when they are finely
divided and in the presence of water and calcium hydroxide (Cal), they react chemically at
room temperature to form cementitious agents [3].

Concrete made from Portland cement is the most widely used construction material today,
mainly due to its cost-benefit ratio, in terms of compressive strength. Its manufacture involves
the release of approximately 900 kg of carbon dioxide per 1000 kg of produced cements.
Likewise, this amount of cement demands the use of 1693 kg of water and 4798 MJ in energy
resources [4]. This is the importance of reducing the environmental impact that the manu-
facture of the same produces. The use of mineral additions in the production of concrete is a
technologically possible alternative. However, its use requires high standards of assurance and
quality assurance, similar to those of cement [5].
The extent of the benefits provided by the use of blended cements increases with increas-
ing content of additives in blended Portland cements. However, the content of additives in
blended Portland cements, especially for natural pozzolans, is limited by some factors, such
as an increase in water requirement and a decrease in the rate of strength development of
the cementitious systems. It has been found that the blended cements containing high vol-
ume (55% by weight) of natural pozzolans (volcanic tuff) possess lower 28-day compres-
sive strength when compared to the reference Portland cement, although they show similar
strength values at 91 days of age [6, 7]. Therefore, the production of high-volume natural poz-
zolan blended cements, which are able to compete against ordinary Portland cement, requires
natural pozzolans exhibiting significantly high-strength activity.

In this chapter, we intend to review the literature available on these topics, addressing struc-
tural, mineralogical, and morphological properties, in the case of zeolites, and manufacturing
processes, characterization, evaluation, and application, in the case of cement. As well each
of the parameters influences the formation of cementing pastes, such as hydration, porosity,
transport properties, durability, and carbonation, among others.

2. Properties of natural zeolite

2.1. Pozzolanic activity surface area

Pozzolans are materials with an amorphous and aluminous siliceous or siliceous content, which
react with calcium hydroxide in the presence of water to form cementitious hydration products
[8]. Among the most common natural pozzolanic materials, such as fly ash and silica fume, is
zeolite, which is used in some regions of the world, due to its lower cost and accessibility [9, 10].
Zeolites generally show pozzolanic activity due to their structural characteristics, and their use
as additions in cements provides additional technical advantages to construction materials [11].

The pozzolanic properties of natural zeolites are determined by their high sorption ability,
ion exchange potential, and specific structure. Their action involves various steps, including
 Characterizations and Industrial Applications for Cement and Concrete Incorporated Natural… 137
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cation exchange; dissolution and/or breakdown of the zeolitic structure; possible formation
of transient gel phases; and precipitation of hydrated calcium silicates and aluminates [12].

There are different methods of work for the evaluation of pozzolanic activity. In general, these
methods are classified as indirect or direct, depending on the parameter to be studied [13].
Direct methods monitor the presence of Ca(OH)2 and its subsequent reduction in abundance
over time, as the pozzolanic reaction proceeds, using analytical methods such as X-ray diffrac-
tion (XRD), thermogravimetric analysis (TGA), or assessment chemistry.
The Frattini test is a commonly used direct method involving chemical titration to determine
the concentrations of Ca2+ and OH− dissolved in a solution containing Portland cement and the
test pozzolan. This method has been used to measure the pozzolanic activity of metakaolin
[14], catalytic cracking residues [15], fly ash [16], and zeolites [17].
The saturated lime method is a simplified version of the Frattini test, in which pozzolan is
mixed with a saturated solution of lime (slaked lime, Ca(OH)2) instead of Portland cement
and water. The amount of lime set by the pozzolan is determined by measuring the residual
dissolved calcium [18].

Indirect test methods measure a physical property of a test sample, which indicates the degree
of pozzolanic activity. This may involve the measurement of properties such as compressive
strength, electrical conductivity, or heat evolution by conduction calorimetry. The results of
an indirect pozzolanic activity test are often corroborated by direct tests to confirm that poz-
zolanic reactions are occurring [19–22].

2.2. Ion exchange

Zeolites naturally occur from volcanic origin and belong to the family of hydrated aluminosili-
cates. Their microporous structures can accommodate a wide variety of cations, which com-
pensate the negative charge created by the substitution of Si by Al. Therefore, natural zeolites
appear as cation exchangers in many applications, thanks to this property. Some of the main
applications of zeolites in this area include the selective treatment of wastewater, extraction of
ammonia, odor control, extraction of heavy metals from nuclear, mining and industrial wastes,
soil conditioning for agricultural use, and even as an additive for animal feedstock [23].

Among all identified zeolites, clinoptilolite is the most abundant natural zeolite. In the structure
of the zeolite, there are three relatively independent components: the aluminosilicate system, the
interchangeable cations, and the zeolitic water. The simplified empirical formula of zeolites is:

M n⁄  Al 2 Si 1−x O 2 .y H 2O

+
x
n
(1)

where x can vary from 0 to 0.5 and Mn+ represents Alkali and alkaline earth metals. The struc-
ture of aluminosilicates is the most conserved and stable component and defines the type of
structure water molecules that can be presented in voids of large cavities and joined between
ion systems and ions interchangeable through aqueous bridges. Water can also serve as a
bridge between interchangeable cations.

The channels of the natural zeolites are predominantly occupied by Na+, K+, Ca2+, and H2O,
as well as traces of Mg2+, Ti4+, Pd2+, K+, and Ba2+. Among them, Na+, K+, Ca2+, and Mg2+ can be
138 Zeolites and Their Applications

exchanged with NH +4 ions. The type and density of interchangeable cations influence the stabil-
ity of the cavities and the thermal behavior of a zeolite [24–27].

2.3. Expansion at elevated temperatures

Concrete is more durable against elevated temperature and fire effects than many other construc-
tion materials. Although ordinary concrete is considered to have a satisfactory fire resistance, it
can lose 40–60% of its original strength upon exposure to 500°C [28]. Bilim [29] reported mortars
containing zeolite show generally better performance to high temperatures about 900°C.
Negative thermal expansion (NTE) is an unusual phenomenon in which materials shrink in
volume when heated (or expand when cooled). It has only been observed in a small number
of solids, including some metallic oxides, cyanide metal, polymers, and zeolites [30]. It is
important to understand how zeolites behave as a function of temperature. In recent years,
research has been carried out on NTE in purely siliceous zeolitic structures [31, 32] and with
a little less attention [31, 33] to aluminum-containing zeolites, in which it is known that struc-
tures and properties are particularly sensitive to extra-structural charge balancing cations and
host molecules in the pores.
Water is an important guest molecule in the pore system of natural and synthetic zeolites.
Adsorbent and catalytic properties of zeolites are also strongly affected by their water content.
Cations seek the most energy-stable positions, and these positions play an important role in
the catalytic activity.
This subject was investigated by Ilić and Wettstein [34], who examined three distinct tem-
perature ranges for volumetric thermal expansion. Associates with the dehydration of coordi-
nated water molecules and with transverse vibrations of bridging oxygen atoms result in the
reduction in the bonding angle.

2.4. Desorption of water at low humidities

As already mentioned, zeolite is a porous solid with a large capacity to house water molecules
and can be used as a pozzolanic aggregate. The efficiency of porous aggregates as an internal
curing agent in concrete depends on its water absorption and desorption characteristics. The
desorption behavior of zeolite and other porous aggregates depends on the structure of their
pores and mainly on the porosity size distribution. In general, a thick pore structure will lead
to better desorption behavior [35–37].
Ghourchian et al. [38] were conducted a study of the performance of the porous aggregates
and concluded that the water desorption of the zeolites is closely related to their microstruc-
ture. For a proper desorption, a thick-pored structure is needed with a high proportion of
well-interconnected pores. While, in the case of zeolites, despite having a high-water adsorp-
tion capacity, they have a fine pore structure, which leads to retaining the water absorbed.

2.5. Re-adsorption of water at high humidities

Zeolites are selective adsorbents for the removal of carbon dioxide, water vapor, and other
impurities from the mixtures. The impurities adversely affect the capacity of the adsorbents
used for the separation or purification. Water is a strongly adsorbed component in zeolite [39].
 Characterizations and Industrial Applications for Cement and Concrete Incorporated Natural… 139
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Due to the nature of the cation exchange, natural zeolites show a high performance in the
adsorption of cations in aqueous solution such as ammonium and heavy metals. However,
zeolites show varied ion selectivity and competitive adsorption for multicomponent system
[27]. In addition, these materials are not good adsorbents for the adsorption of anionic and
organic ions. Surface modification with cationic surfactant can change the surface charge
of the natural zeolite, making them applicable for adsorption of anions and organics. Most
zeolites when heated give off water continuously rather than in separate stages at certain
temperatures. The dehydrated zeolite can then reabsorb the original amount of water when
exposed to water vapor. Recent investigation has shown that some zeolites such as phillipsite
and gismondite lose and gain water in a stepwise manner. All-silica zeolites are chemically
and hydrothermally more stable than aluminum containing ones and are therefore preferred
for membrane application, including for dehydration, even though these types of membranes
are hydrophobic [40].
The adsorption characteristics of any zeolite depend on the detailed chemical/structural com-
position of the adsorbent. The Si/Al ratio, the type of cation, the number, and the location
are particularly influential in the adsorption. These properties can be modified by various
chemical treatments to improve the separation efficiency of the natural raw zeolite. Acid/base
treatment and impregnation with surfactant by ion exchange are commonly used to change
the hydrophilic/hydrophobic properties for the adsorption of various ions or organic [27].

3. Effects of natural zeolite on the properties of cement and concrete

composites

3.1. Mechanical properties

In general, the higher the cement replacement by natural zeolite has the lower the compres-
sive strength. However, the percentages of reduction in resistance generally decrease with
increasing age in cement. This behavior may be related to the pozzolanic activity of the natu-
ral zeolite. In terms of compressive strength, it appears that natural zeolite performs better in
mixed cement compounds with lower water-cementitious material (w/cm) ratio [41].

In term of compressive strength, it seems that natural zeolite performs better in blended
cement composites with lower w/cm ratios. Ahmadi and Shekarchi [42] showed that the
concretes containing natural zeolite with a w/cm ratio of 0.40 displayed higher compressive
strength than the control mixture at the ages of 3, 7, 28, and 90 days, whereas contrary results
were obtained for the concretes with a w/cm ratio of 0.5 in the present study. Markiv et al.
[43] showed, recently, that the substitution of cement by zeolite resulted in some reduction
in strength until 90 days of hardening, but after 180 days, compressive strength of concretes
containing zeolite exceeds the strength of concrete without zeolite.

Uzal and Turanlı [44] reported the similar compressive strength of mortar with 55% zeolite
in the binder to that of 100% Portland cement mortar, but this could only be achieved using
superplasticizers. Karakurt and Topçu [45] found 30% replacement of Portland cement by
zeolite in their blended cement mortars as optimum; the compressive strength was similar to
the reference mortar. Valipour et al. [46] observed a fast decrease in the compressive strength
140 Zeolites and Their Applications

of concrete with the increasing amount of zeolite (10–30% of the mass of Portland cement) in
the mix, even with an increasing superplasticizer dosage.

3.2. Alkali-silica reaction

It is generally recognized that the addition of pozzolan reduces the calcium hydroxide con-
tent in cement paste and improves the permeability of concrete [47]. The most important con-
cerns in the design of durable concrete are the alkali-silica reaction (ASR) and sulfate attack.
ASR causes the premature deterioration in concrete. Alkali hydroxides present in the con-
crete pore solution react with amorphous or poorly crystalline silica phases in aggregates,
forming a gel that imbibes water and expands [48]. The expansive pressure generated by
the hydrated alkali silicate has been widely believed to induce cracking and deterioration of
concrete. However, this notion may not be necessarily correct. Concrete is a porous material,
and the hydrated alkali silicate is rheologically a fluid material that can slowly diffuse into
the pores and preexisting cracks to lose its expansive pressure. The diffused alkali silicate has
been proposed to generate an expansive pressure by reacting with Ca2+ ions [49].

3.3. Transport properties

The transport properties of concrete with the addition of zeolite have been studied by Ahmadi
and Shekarchi [42] and Najimi et al. [41], who found a significant reduction in the penetration
of water and chlorides, in the concrete with natural zeolite. On the other hand, Valipour et al.
[50] reported that water sorptivity and gas permeability increase with the increase of zeolite
in the mixture. Similar results were obtained for the oxygen permeability of Ahmadi and
Shekarchi [42] but only for the dose of zeolite greater than 10%.
The liquid water transport parameters increase with the increasing addition of zeolite in the
mixed binder. This is due to the pore distribution, that is, the volume of capillary pores, which
is the most important factor, in the capacity of a porous medium to transport water in liquid
form. In studies conducted by Vejmelková et al. [51], it was found that, for lower zeolitic con-
tents, up to 20%, the values of water absorption coefficient and apparent moisture diffusivity
were still acceptable. However, for high levels of cement replacement, the acceleration of water
transport is so high that it could present a concrete durability risk.

Ahmadi et al. [52] reported that natural zeolitic addition in concrete results in better water
absorption, water penetration, and electrical resistivity, and the ternary mixtures containing
natural zeolite with silica fume or fly ash perform best in water permeability and chloride
penetration tests.

3.4. Durability properties

3.4.1. Sulfate and acid attack resistance

The durability of a concrete is a determining feature for its use, and this is due to the different
corrosive environments to which it is exposed, including marine construction or hydraulic
engineering. One of the important factors of this characteristic of concrete is the type of cement.
 Characterizations and Industrial Applications for Cement and Concrete Incorporated Natural… 141
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It has been shown that the use of pozzolanic additives for cements increases their resistance
to corrosion, due to the high impermeability, the decrease in the content of Ca(OH)2, and the
reduction in the presence of capillary pores in the matrix. In fact, it hinders the penetration
of aggressive media [53]. Concrete can be attacked by acids both internally and externally.
The existence of different kinds of acid in the environment around the concrete causes a great
reduction in the pH of the concrete, and the reaction between the acids and the hydrated and
unhydrated cement finally leads to the deterioration of the concrete. The primary effect of any
type of acid attack on concrete is the dissolution of the cement paste matrix [54].

Małolepszy and Grabowska [55] carried out a study dedicated to studying the sulfate resis-
tance of a cementing paste with zeolitic addition. They confirmed the beneficial effect of
the zeolitic additive for cement mortars because those containing zeolite did not show vis-
ible damage in the surface in an aggressive solution of sulfate, while in the mortar that did
not possess it, I present surface microcracks pronounced. Exfoliation of corners and colors
changes (yellow and gray incursions on the walls of the samples).

3.4.2. Drying shrinkage

The contraction is a phenomenon in which the concrete reduces its volume with time. The
internal and external drying of the concrete is the main factor that causes the contraction.
Internal drying, also known as self-desiccation, is caused by the consumption of water in the
hydrating cement paste and the resulting creation of interfacial menisci between the pore
fluid and the vapor in progressively smaller pores [56]. The creation of meniscus leads to the
accumulation of capillary pressure that puts the solids under compression and causes a mac-
roscopic contraction, called autogenous contraction [56, 57]. External drying takes place due
to the evaporation of water from the surface of the concrete to the ambient air or due to the
migration of water to adjacent members. The evaporation of moisture from the surface of the
fresh concrete can cause cracking of the plastic shrinkage [58], and a greater moisture loss of
the hardened concrete can cause shrinkage by drying [59].

Generally, the durability properties of concrete improved by partial replacement of cement

with natural zeolite. However, the concrete that contains 15% of natural zeolite achieves a
suitable drying shrinkage. The latter does not have a satisfactory performance in the acid
environment [41].

3.4.3. Freeze and thaw resistance

The pores can have an effect on the properties of the material in different ways. The compres-
sive strength is primarily related to the total porosity, the size of pores and their distribution,
the size and form of the biggest pores, and the relation between the pores. Shrinking is the
function of energy exchange on the surface of pore walls. Durability depends on freeze-thaw
resistance and is controlled by the volume of air entrained in the pores and spaces between
the pores [60].

Water absorption and freeze-thaw resistance of hardened cement paste depend on the size of
pores and capillaries, their type and distribution, and the closing of the pores. Closed and small
142 Zeolites and Their Applications

pores are not filled with water completely. Pores that are not filled up with water are called
reserve pores. In freezing conditions, some water from fully filled pores may move to these
reserve pores and thus create a space for ice expansion. The distance between filled and unfilled
pores must be small, so that the freezing water would move from filled to unfilled pores [60].
Capillary pores in hardened cement paste are formed through the evaporation of excessive
water used in producing the cement paste. Usually, the cement paste is made using more
water, and it is necessary for chemical reactions that occur during the setting of concrete.
According to A. K. Kallipi, capillary pores are open and easily fill with water. The destruc-
tive effect during freezing depends on the amount of water in hardened cement paste.
Presumably, the bigger amount and size of the pores reduce the freeze-thaw resistance of
concrete. Furthermore, it is important to mention that the concrete prepared with saturated
and dry recycled aggregates exhibits poorer freeze-thaw resistance, whereas better results
obtained from the concrete made with the semi-saturated aggregates [61].

3.4.4. Carbonation

When a cementitious paste begins to harden with an air cure, and after the first minute of hydra-
tion, it is subjected to the action of carbon dioxide ions (CO 3− 2 ) contained in the air, which reacts
with Ca 2+ ions of the portlandite, ettringite, and the silica gel of calcium in the form of Ca-carbonates
(CaCO 3). This carbonation of the hydrate products is provided in the following schemes [62]:

Ca (OH) 2 + CO 2 → CaCO 3 + H 2O, (2)

3CaO ∙ 2Si O 2 ∙ 3 H 2O + 3CO 2 → 3CaCO 3 + 2Si O 2 + 3H 2O, (3)

3CaO ∙ Al 2O 3 ∙ 3CaSO 4 ∙ 32 H 2O + 3CO 2 → 3CaC O 3 + 3(CaS O 4 ∙ 2 H 2 O)

+ Al 2O ∙ x H 2O + (26 − x) H 2O (4)

The air-curing conditions normally increase carbonation and cause incomplete hydration,
self-neutralization, and drying shrinkage. These effects are most probably caused by decreas-
ing the capacity for retaining sufficient water during the hydration and pozzolanic reactions.
The depth of the carbonate layer formed depends on the contact time with C O 2 and its con-
centration in the surrounding environment as well as the diffusion coefficient of the hardened
cement paste [63–65]. As the air-curing conditions are more important for long-term reactions
than for short-term ones, the C2S phase, which usually reacts after 21 days, is the most read-
ily affected cement phase. The volume changes, which accompany the carbonation processes,
lead to the filling of empty pore volumes with Ca carbonates and densify the structure of the
hardened cement paste. Groves et al. [66], the microstructure of hardened pastes of C 3 S and a
smoke mixture of C 3 S/silica by TEM, before and after partial carbonation in a pure CO 2 atmo-
sphere, concluded that calcium carbonate forms mainly in the outer product regions such as
microcrystalline vaterite or calcite, which leads to a substantial level of carbonation of pulp in
a day with a little additional carbonation in the coming days. The depth of penetration of Ca 
CO 3 in the cement matrix depends on the time of contact of carbon dioxide and its concentra-
tion in the medium and on the coefficient of diffusion [67].
 Characterizations and Industrial Applications for Cement and Concrete Incorporated Natural… 143
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Lilkov et al. [62] have studied the early hydration of the cement, mixed with additives of natu-
ral zeolite (clinoptilolite), and they concluded that the process of carbonation on the surface of
the cement paste takes place directly between the calcium ions of the solution and the carbon
dioxide of the air without the formation of portlandite and ettringite. The depth of the carbon-
ate layer formed depends on the contact time with the CO 2 and the rate of diffusion through
the formed layer, where the crystallite size of the calcite is reduced overtime days.

3.4.5. Corrosion of steel reinforcement

The main causes of reinforcing steel corrosion are reacted with various aggressive agents,
such as atmospheric carbon dioxide and chloride ions, and chemical attack throughout the
service life of the concrete [68]. In ordinary Portland cement, these harmful effects can be
reduced by substitute pozzolans [69]. Under a corrosive environment, concrete properties can
be improved by using pozzolans such as zeolite and diatomite [68].

Steel rebars are protected against corrosion by both chemical and physical mechanisms. The
chemical protection is provided by the concrete high pH (12–13), which promotes the for-
mation of a passive film on the steel surface. On the other hand, concrete acts as a physical
barrier, hindering the access of aggressive agents. However, oxygen, water, chlorides, and/
or carbon dioxide can be transported through concrete, reaching the rebars and inducing the
corrosion attack. The chloride ions, when above a threshold value, provoke a local breakdown
of the passive film and pitting corrosion. Carbon dioxide and its hydrolysis products react
with the alkaline species present in concrete, leading to pH values as low as 9 [70].
Ahmadi and Shekarchi [42] found a positive effect of zeolite in cement mortar on the resis-
tance to alkali-silica reaction. Janotka and Krajči [71] reported an improvement of sulfate
corrosion resistance of zeolite-containing concrete. Similar effects of zeolite on alkali-silica
reaction and sulfate resistance were observed by Karakurt and Topçu [45]. On the other hand,
Najimi et al. [41] reported a significant strength reduction of zeolitic concrete after exposure to
sulfuric-acid environment, that is, ~20% after 356 days when compared with ~5% for reference
Portland-cement concrete.

3.4.6. Chloride-induced corrosion

Besides eco-friendly, concrete should be sustainable and durable due to its use in infrastruc-
ture applications, which are mostly in aggressive environments, such as harsh marine envi-
ronments with highly possible chloride-induced corrosion. Valipour et al. [72] reported that
natural zeolite from a durability point of view in harsh marine environments could be a good
option for replacement of cement even comparing with metakaolin and silica fume, which
would be beneficial even from environmentally friendly point of view. Because concrete con-
taining 20% replacement level in splash exposure showed chloride diffusion resistance even
better than metakaolin with 5% replacement level and silica fume with 5 and 7.5% replace-
ment level.
Several studies have indicated that lowering the w/b ratio and adding different types of poz-
zolanic materials to the mix can improve the compressive strength, durability, and permeabil-
ity of concrete. Lowering the w/b ratio reduces the porosity, which thereby reduces chloride
144 Zeolites and Their Applications

ingress during the exposure period by as much as 25% [46]. Moreover, pozzolanic materials
are being used widely as mineral admixtures to enhance the mechanical properties of con-
crete and thereby improve the concrete’s microstructure. These admixtures, either natural
or artificial, reduce the Ca(OH)2 content produced during the cement hydration process and
instead form C─S─H gel through the secondary reactions. This process retards the hydration
process, significantly reducing the porosity and permeability of the concrete [73–75].
Valipour et al. [76] found that the partial replacement of cement by 10 and 20% natural zeolite
drives a higher compressive strength at 28 days, while 30% zeolitic replacement decrease
the compressive strength when compared with conventional concrete. Moreover, the use of
natural zeolite to improve the durability of concrete in aggressive environments, such as the
Persian Gulf, results in a concrete with appreciably low chloride permeability.

3.4.7. Heat of hydration

Nowadays, there is a discussion concerning the role of natural zeolitic effects on the blended
cement hydration during the time. During the early stage of hydration, the effects of zeolite
are related to the critical role played by their structure and the large surface area of the parti-
cles determining the cation ability in the pore solution and the collateral effect on stimulation
of Portland cement hydration due to the low reaction degree of the zeolite [77]. The later stage
is the proper pozzolanic reaction between the CH liberated during the hydration of cement
and the soluble SiO2 and Al2O3 present in bulk zeolite occur after 2 weeks producing com-
pounds with cementing properties [78, 79]. Some zeolites are thermally activated [80]. Özen
et al. [10], Cornejo et al. [81], and García de Lomas et al. [82] studied the early-age hydration
heat of Portland cement blended with a spent zeolite catalyst in an amount of up to 35% of the
mass of cement, but the composition of the applied catalysts was significantly different from
the natural zeolite. Caputo et al. [83] analyzed the hydration heat development in natural
zeolite samples mixed with portlandite in a 1:1 ratio.
Furthermore, Tydlitát et al. [84] concluded that natural zeolite did not react during the early
age, but it causes the acceleration of cement phase’s hydration. Hence, the early effects of
zeolitic addition depend on their physical and chemical characteristics, and it also depends
on the Portland cement composition.

4. Application of natural zeolite as pozzolan in cement and concrete

composites

4.1. Characteristic

Supplementary cementitious materials (SCMs) are natural or by-product materials, which

react with Ca(OH)2, (CH), and form hydraulic compounds, such as hydrated calcium silicate
hydrate (C─S─H) and calcium aluminate hydrate (C─A─H) [1]. Natural zeolite belongs to the
group of natural SCM, whose pozzolanic activity depends on several factors (chemical and
mineralogical composition, particle size distribution, specific surface area, cation-exchange
capacity, Si/Al ratio of the zeolite framework, etc.) [77]. Each of these factors provides unique
characteristics to each cement mix.
 Characterizations and Industrial Applications for Cement and Concrete Incorporated Natural… 145
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In the previous studies concerning the use of zeolites in concrete production, one of the most
frequent topics was their pozzolanic activity as a fundamental condition for their utilization
as supplementary cementitious materials (SCMs). Perraki et al. [77] reported a good pozzo-
lanic reactivity of zeolite, 0.555 g of Ca(OH)2 per 1 g of zeolite according to the Chapelle test.
Ahmadi and Shekarchi [42] found out that the pozzolanic activity of zeolite was lower than
silica fume but higher than fly ash.

Many studies have promoted the use of the zeolite-bearing tuffs as SCMs due to their positive
influence on the long-term compressive strength and durability. Nevertheless, the variability
in tuff’s mineralogical and physical properties results in limited understanding of pozzolanic
activity of natural zeolites.
When zeolite is added to the cement, at a level of around 10%, some characteristics are modi-
fied, such as, an increase in compressive strength [43, 85], a decrease in pore size [86, 87], and
an increase in corrosion resistance to the acid solution [55, 88].

4.2. Proper incorporation

Many authors have talked about the appropriate amount of zeolite that must be incorporated
into the cement, so that it improves its properties or it can maintain them. Najimi et al. [41]
found out that incorporation of 15% natural zeolite in the blended binder improved compres-
sive strength of concrete, but for concrete with 30% zeolitic content, they observed a 25%
strength decrease even with adding a superplasticizer, which was not used in the reference
mix; they concluded that concretes incorporating zeolite are characterized by the reduction in
the heat of hydration and consequently of thermal cracking; and they also improved durabil-
ity properties such as chloride ion penetration, corrosion rate, drying shrinkage, and water
penetration. Ahmadi and Shekarchi [42] also reported that the incorporation of natural zeo-
lite as a mineral admixture in concrete enhanced its durability properties. However, various
types, structures, and purities of natural zeolites influence concrete strength and durability
in different ways and can lead in some cases to contradictory results in experimental studies
and observed an increase in compressive strength for up to 20% of natural zeolite used as
Portland cement replacement, but this was achieved with an increasing amount of super-
plasticizer in the mixes containing zeolites. Uzal and Turanli [44] reported the similar com-
pressive strength of mortar with 55% zeolite in the binder to that of 100% Portland cement
mortar, but once again, this could only be achieved using superplasticizers; they describe
that a lime reactivity of the clinoptilolite zeolite is comparable to silica fume, higher than fly
ash and a non-zeolitic natural pozzolan. Therefore, calcium hydroxide as a cement hydration
product combines with natural zeolite consisting of reactive SiO2 and Al2O3 to form calcium
hydrosilicates. Karakurt and Topçu [88] found 30% replacement of Portland cement by zeo-
lite in their blended cement mortars as optimum; the compressive strength was similar to the
reference mortar. Valipour et al. [50] observed a fast decrease in the compressive strength of
concrete with the increasing amount of zeolite (10–30% of the mass of Portland cement) in the
mix, even with an increasing superplasticizer dosage. Investigations of mechanical proper-
ties of concretes show that the substitution of cement by zeolite resulted in some reduction
in strength until 90 days of hardening, but after 180 days, compressive strength of concretes
containing zeolite exceeds the strength of concrete without zeolite. Introduction of zeolite
and chemical admixtures in concrete permits the modifications of the phase composition of
146 Zeolites and Their Applications

cement hydration products with the formation of an extra amount of calcium hydrosilicates,
hydrogelenite, and ettringite [43].

4.3. Influencing parameters

Najimi et al. [41] concluded that concretes incorporating zeolite are characterized by the
reduction of the heat of hydration and consequently of thermal cracking and improved dura-
bility properties such as chloride ion penetration, corrosion rate, drying shrinkage, and water
penetration. Sabet et al. [89] and Ahmadi and Shekarchi [42] also reported that the incorpo-
ration of natural zeolite as a mineral admixture in concrete enhanced its durability proper-
ties. However, various types, structures, and purities of natural zeolites influence concrete
strength and durability in different ways and can lead in some cases to contradictory results
in experimental studies.

Uzal and Turanli [44] reported that the type of major cation was found to be one of the proba-
ble factors governing the pozzolanic activity of clinoptilolite zeolites by affecting their degree
of solubility in alkaline conditions. Experimentally demonstrated that pastes of blended
cements containing a large amount of clinoptilolite tuff contain less amount of pores >50 nm
when compared with Portland cement paste, which is beneficial in terms of mechanical
strength and impermeability of the pastes.

4.4. Elaboration methods

The methods of preparation of cement mixtures with zeolite vary according to the type
of study and parameter that is intended to know, and this is due to the constant search to
improve their properties. However, there are regulations that help to delimit the use and
management of pozzolans, this, if it is intended that the study has a commercial impact, or
that meets the standards established for the development of mortars (Table 1).
Several authors have investigated how to improve the mechanical properties of cement with zeo-
lite, and its resistance to compression is specific. Valipour et al. [50] and Chan [90] were agreed
that, to improve this characteristic, cement mixtures should not exceed 45% of zeolitic addition.
While if what is desired is to avoid the carbonation process of the cement, the additions should

Name Scope
ASTM C-618 Standard specification for coal fly ash and raw or calcined natural pozzolan for use in concrete

ASTM C-191 Standard test methods for time of setting of hydraulic cement by the Vicat needle

ASTM C-33 Standard specification for concrete aggregates

ASTM C-311 Standard test methods for sampling and testing fly ash or natural pozzolans for use in Portland-
cement concrete

ASTM C-1202 Standard test method for electrical indication of concrete’s ability to resist chloride ion
penetration

ASTM C-876 Standard test method for corrosion potentials of uncoated reinforcing steel in concrete

ASTM C150 Standard specification for Portland cement

Table 1. Standard specifications by ASTM.

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not exceed 30% [62, 91, 92] because this process is more evident in the early hydration phase, but
it reduces with the passage of time. It is necessary to consider that the hydration of the cement is
perhaps the most important aspect because it will derive almost all the processes addressed in
this article, besides being a determining factor in the cementing process of the mixture. Several
researchers [84, 93, 94] concluded that the addition of zeolite to the cement paste greatly increases
the early stage of hydration, and therefore, it is not recommended to exceed 40% of pozzolanic
addition in the mixture. In this way, operational parameters that contribute to the development
of a composite mix with the best features and operational performance can be established.

It is not enough to establish limits in the substitution of cement with pozzolans because the
structure of the zeolite also plays a very important role in the interaction with the mixture;
as already mentioned, there is a great variety of zeolites, each with its respective family and
structure [95], and the treatment that each one must receive before its incorporation into the
cementing pastes can be very different. First, it must be understood that the Si/Al ratio will
define the homogeneity of the mixture and the setting process [96] with a higher percentage of
alumina in their structure that will tend to have a weaker and slower setting, while those that
have a very large pore diameter will facilitate the carbonation of the mixtures. There are many
ways to incorporate zeolite to cement pastes, but they have in common the amorphization of the
same, whether, by mechanical, chemical, or thermal methods, the main objective is to generate a
correct balance between the Portland cement and the percentage of Si/Al content in the zeolite.

The dealumination is one of the most widespread methods for the control of the percentage Si/
Al present in the zeolite and encompasses the aforementioned methods. In 1968, McDaniel and
Maher prepared the ultra-stable Y zeolite by combining procedures for the exchange of sodium
ions with ammonium and hydrothermal treatments at elevated temperatures (T ≥ 600°C). Under
the conditions of “deep bed,” these treatments caused the removal of structural Al with the con-
sequent decrease of the cell parameter. On the contrary, when the hydrothermal treatment was
carried out in a “shallow bed,” the protonated form of the zeolite was obtained without causing
dealumination. It has been possible to dealuminate up to 98% Y zeolite by hydrothermal treat-
ments without an appreciable loss of crystallinity.

In 1968, Kerr developed a method to dealuminate Y zeolites at low temperature (around

100°C) by using a hydrolyzing and complexing agent of aluminum such as EDTA [97] with this
method; however, you cannot dealuminate above 70% without drastic losses of crystallinity.

Subsequently, the use of SiCl4 at high temperatures was reported to dealuminate Y-type zeo-
lites in a single step, quickly and with percentages of Al removal that could reach values above
90% [98].

Finally, Skeels and Breck reported a procedure in which ammonium hexafluorosilicate is

used as a deadening agent, under mild conditions at low temperatures. It is a quick and
simple method, but the superior level of dealumination, as with EDTA, is limited to 70% to
avoid crystalline collapse.

4.5. Textural and mechanical characterization

The textural characterization of the zeolite-cement compound consists of measuring the pore
size present in the element; the analysis of this porosity has as an objective to measure the
surface of the pores and the volume of the same. It should be mentioned that the compound
148 Zeolites and Their Applications

may have microporosity or mesoporosity; as the study by Franus et al. [99], there are several
ways to calculate the volume, distribution, and surface area of the pores among which are
the general isotherm equation based on the combination of a modified Kelvin equation and a
statistic thickness of the adsorbed film and the multilayer adsorption theory [100].
The mechanical characterization performed on cement pastes with zeolitic content does not
differ from the typical mechanical compression tests (performed to see the maximum load
before causing a fracture), which are carried out by means of a universal machine. However,
both the size of the specimens and the laboratory conditions (temperature, pressure, and per-
centage of aggregates) depend on the author and the results that he intends to obtain. There is
a lot of research on the mechanical state of the test tubes [41, 51, 99, 101], and it is important to
mention that in most of them, the state of operation is evaluated after having been subjected
to adverse media, such as chloride attack or exposure to acid media.

4.6. Special applications of these composites

At present, due to the many investigations that exist on cement with zeolitic addition, we can
find large areas of opportunity for its application. However, its use as a cement for construc-
tion is the most researched application [9, 41, 93, 96], and this is obvious when the main func-
tion of this compound is to work as an alternative to ordinary cement (usually the Portland
type) in the cement industry building. Although there are other applications of the same scope
and not so obvious, which have not been given the same attention, among them we can find
its use for the stabilization of sandy soils prior to the construction of roads [102, 103], agent
for the reduction in pollutants and environmental conditions [76, 104], and its application in
cementing operations carried out on the high seas and oil platforms [46, 105].

5. Concluding remarks

The partial replacement of cement is a fact that every day becomes more important; it is an
activity that is already carried out and that although there are few cement producers that com-
mercialize with these compounds, it is a great step for the reduction in emissions of CO2. Many
authors have contributed and are still investigating the properties that this mixture provides
us in order to improve them and to be able to develop a mixed cement paste that is capable
of equalizing the effectiveness of Portland cement, which although it is close to it, in the case
of zeolite as a pozzolan, it has not yet been achieved that this represents 50% of the mixture.
Fortunately, with the growing research and development of new methods for the synthesis
and management of these minerals, achieving a balance between the costs of production and
the effectiveness of the product can be a reality. It should be mentioned that the use of zeolite
as a pozzolan is not a whim, and although it competes with other pozzolans that can deliver
a better mechanical performance such as silica fume and volcanic ash, the possible produc-
tion savings due to availability and improvement from other areas such as resistance to car-
bonation, transport properties, hydration of the mixture, and absorption of contaminants are
concepts that are worth investigating and investing for their development and improvement.
 Characterizations and Industrial Applications for Cement and Concrete Incorporated Natural… 149
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Author details

Iván Ayoseth Chulines Domínguez1, Youness Abdellaoui2, Mohamed Abatal1* and

Cristóbal Patiño-Carachure1

*Address all correspondence to: [email protected]

1 Facultad de Ingeniería, Universidad Autónoma del Carmen, Ciudad del Carmen,
Campeche, Mexico
2 Universidad Autónoma de Yucatán Facultad de Ingeniería, Mérida, Yucatán, Mexico

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