Construction and Building Materials 140 (2017) 10–19

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Construction and Building Materials

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Review

Processing, effect and reactivity assessment of artificial pozzolans

obtained from clays and clay wastes: A review
Siline Mohammed
Laboratory of Materials and Mechanics of Structures (LMMS), University of M’sila, Algeria

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Clays, clays wastes and clay wastes

initially treated can lead to pozzolans.

In these materials, phyllite minerals
are at the origin of this pozzolanicity.

To elaborate an APC, the treated
material must be totally
dehydroxylated.

Clay wastes mineralogical variety
make difficult to elaborate a high
reactive APCW.

In the APCWIT case, the initial
treatment uncertainty is the major
disadvantage.

a r t i c l e i n f o a b s t r a c t

Article history: The blended Portland cement, CEM II, is obtained by replacing a part of clinker by an addition, as
Received 10 August 2016 described in the EN 197-1 standard. Among the materials cited in this standard, there are the artificial
Received in revised form 7 January 2017 pozzolans. When used as partial replacement of clinker or cement and in presence of water, the poz-
Accepted 15 February 2017
zolanic materials react with the calcium hydroxide Ca(OH)2. This reaction leads to a Supplementary
Cementitious Compounds SCC (C-S-H, CAH, CASH) comparable to those formed during the ordinary
cement hydration. Treated clays are an artificial pozzolans widely studied in the last years. It is known
Keywords:
that these materials are essentially composed from phyllosilicates, quartz, carbonates, etc. As the poz-
Clay minerals
Dehydroxylation
zolanic reactivity depends mainly of phyllite minerals, several features must be taken into consideration,
Portlandite especially the dehydroxylation rate. Generally, the dehydroxylation is obtained by thermal treatment,
Pozzolanicity which varies from clay to another. Recent studies have shown that the use of treated clays may lead
Cement to improvements in mortars and concretes properties, whether at the fresh state or the hardened one.
The assessment of these improvements is often conducted by many techniques and tests allowing to esti-
mate the treated clays pozzolanicity. This paper presents an overview of the literature related to the elab-
oration, the utilization, the efficiency and the pozzolanicity tests of some clay minerals and wastes used
as reactive additions in blended cements.
Ó 2017 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2. Elaboration of artificial pozzolans from clays and clay wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1. Some required properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

E-mail address: silinemohammed@gmail.com

http://dx.doi.org/10.1016/j.conbuildmat.2017.02.078
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
 S. Mohammed / Construction and Building Materials 140 (2017) 10–19 11

2.2. Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.3. Mechanisms of pozzolanic reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3. Effects of artificial pozzolans on mortar and concrete properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4. Test methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.1. Chemical tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.1.1. Frattini tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.1.2. Saturated lime test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.2. Physical methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.3. Mechanical tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.4. Comparison between tests of pozzolanicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

1. Introduction carbonates, feldspars and metal oxides. Phyllosilicates are a large

The Portland cement is a powdery substance made from some
naturally occurring minerals, mainly contained in limestone and
clay. In this mix, CaO is the major component, while oxides: SiO2,
Al2O3 and Fe2O3 are supplied by the clay, initially used at about
20%. After grinding, the raw meal is burned at around 1450 °C,
where, chemical reactions take place to form the clinker, which
contains, essentially, calcium silicates (C3S, C2S) and aluminates
(C3A, C4AF). During the cement production process, CO2 is emitted
by two different sources: the CaCO3 decomposition (decarbona-
tion) and the combustion of fossil fuel (during the burning).
Cement manufacturing is considered to be one of the highest car-
bon dioxide emitting industries in the world by emitting almost
0.83 kg of CO2 per each kg of cement produced [1]. This industry
generates approximately 5% of anthropogenic CO2 in the world
[2] and can reach 8%, according to Kajaste [3]. Among the solutions
proposed to reduce this level of CO2 emissions from cement pro-
duction, we cite: the use of blended Portland cement, in which
we proceed to the partial substitution of clinker by some additions.
Pozzolanic additions are widely studied in the last decades.
These supplementary cementitious materials (SCMs) may be used
as a substitution of clinker [4,5], or cement [6]. Whatsoever natural
[7] or artificial [8], these materials are used to improve some char-
acteristics of mortars as strength [9], durability [6], rheological and
transfer properties [10]. The enhancement of these properties is
linked to the reactivity of these additions leading to a Supplemen-
tary Cementitious Compounds SCC (chemical pozzolanicity) [11],
but also to their fineness (physical pozzolanicity) [12].
As artificial pozzolanic additions there are two types: by-
products such as fly ash and silica fume [6] and treated clays where
the most known is Metakaolin. The Metakaolin is obtained from a
kaolinitic clay after heat treatment between 500 and 900 °C. It has
attracted the interest of several researchers [13–15] and was the
subject of the NF P-18 513 standard. Some other clays may lead
to artificial pozzolans, they must subjected to treatment (thermal
in usually), ensuring a maximum of dehydroxylation, without
recrystallization. This is the case of illite [16,17], smectite [18,19],
bentonite [20], muscovite [21], montmorillonite [16,22], chlorite
[23], sepiolite [24], low-purity mica clay [25], etc. Besides the
exploitation of natural resources, recent studies have shown that
it is possible to obtain artificial pozzolans from some sludges (after
treatment) such as: dams [26,27], water treatment plants [28],
paper industry [29], and wastes (without treatment) such as: brick,
tile, marble and ceramic industries [30–32]. These materials have
received lesser attention, probably because of their lower reactivity
and subsequently lower performance as SCMs in cement blends
[19].
It is known that the clays are mixtures of clay minerals (phyl-
losilicates) and clay crystals of other passive phases such as quartz,
family of minerals that commonly show layered structures [33].
Phyllosilicates, mostly composed of silica and alumina, present a
sharp pozzolanic activity when calcined and ground to cement-
fine [34]. If they are well thermally-treated, these minerals lose
their crystallinity, and became able to release reactive silica and
alumina leading to SCC production by consumption of Portlandite.
To understand artificial pozzolans elaborated from clays, knowl-
edge of clay minerals is indispensable.
Clay minerals may be classified according to their layered struc-
ture as types 1:1 or 2:1 (Fig. 1). Each layer is fundamentally built of
one or two tetrahedral silicate (Si-O) sheets and one octahedral
metal (Mg2+ or Al3+) – oxide or hydroxide (M-O or M-OH) sheet.
The 1:1-class clay mineral consists of one tetrahedral sheet and
one octahedral sheet, like kaolinite and serpentine. However, the
2:1-class is composed of an octahedral sheet sandwiched between
two tetrahedral silicate sheets, like vermiculite, montmorillonite
and sepiolite [33]. Some atoms (Si, Mg and Al) can be substituted
for other atoms, which induce negative charges all over the layers.
As a result of these negative charges, interlayer cations (K+, Ca2+,
Na+, etc.) must be absorbed.
Clay wastes can be classified into two categories, (i): Clay
wastes (CW) requiring a treatment, like marine sediments, sludge
of dams, water treatment plants, etc. (ii) clay wastes initially heat
treated (CWIT), we cite: wastes of brick, ceramic or tile.
At the raw state, the clay has two kinds of water: physically
bound (adsorbed) and chemically bound which takes the form of
hydroxyls in the clay phyllite minerals. The efficiency of artificial
pozzolans obtained from clays (APC) or from clay wastes (APCW)
depends on the removal level, by treatment, of the chemically
bound water (dehydroxylation). The total dehydroxylation corre-
sponds to the destruction of these minerals crystallinity, which
confers them an amorphous state and a pozzolanic reactivity.
However, the reactivity of artificial pozzolans obtained from clay
wastes initially treated (APCWIT) is difficult to be controlled, due
to their inappropriate treatments.
The use of clays and clay wastes, as pozzolanic additions in
cement industry, is well known throughout the world. While
(APCW) and (APCWIT) are still under study and not yet normalized
or commercialized, the industry of (APC) is widely developed espe-
cially for Metakaolin. In France, since 1983 the annual production
of MK is 200,000 tonnes. The material, commercialized under the
NF P18-513 standard, has already been used in many projects,
including the bridge Chaban-Delmas in Bordeaux. However, the
world’s total output of kaolin exceeds 25 million tonnes [35].
According to Mirovic et al. [8], a large kaolin clay deposit of about
55 million tonnes, is located in ‘‘Garaši” basin in Serbia and not yet
exploited. Haili Cheng [36] reported that more than 20 billion m3
of clay brick products, produced in China in the past five decades,
will mostly be transformed into clay wastes in the next five
12 S. Mohammed / Construction and Building Materials 140 (2017) 10–19
Fig. 1. Classification of some phyllite clay minerals.
decades. In Algeria, Chikouche et al. [26], reported that more than
45 Mm3 of sludge and clay wastes invade annually, only, nine dams
in the country.
At an environmental point of view, the use of clays and clay
wastes presents an efficient solution to reduce the CO2 emissions
related to the cement industry [37]. The thermal process, used to
elaborate artificial pozzolans from these materials, releases much
less of CO2 than clinker. The emitted CO2 rate depends mainly on
the carbonates level in the raw clays and clay wastes. Other pro-
cesses, such as mechanical and chemical, may lead to CO2 emission
rates close to zero. For the (APCWIT) and according to statistics, the
brick industry can generate 180 kg of CO2/tonne of brick, which is 5
times lower than that due to the clinker formation.
At an economic point of view, the cement manufacture con-
sumes considerable amounts of energy during the clinker forma-
tion and for its grinding. Clays and clay wastes present an
efficient solution to obtain economic cement. Hamidi et al. [38]
reported that the total energy required to produce one ton of
cement is at least 750 kW h. They demonstrated that the calcina-
tion of an andesite at 800 °C needs only 500 kW h per ton of this
clay. For the grinding energy, contrary to the authors finding in this
case of andesite, most clays and clay wastes are more fragile than
clinker, hence a decrease in grinding energy may be obtained. The
(APCWIT) are the most economical and require only the grinding
energy. This paper sets out to review the elaboration, the effect
and the reactivity tests of these artificial pozzolans.
2. Elaboration of artificial pozzolans from clays and clay wastes
2.1. Some required properties
To elaborate an APC or an APCW we must carry out a treatment
on the raw material, but before, it must satisfy certain chemical
and physical conditions. It is known that pozzolanic activity
depends mainly on the clay content from (SiO2) and (Al2O3). That’s
why the European standard EN 197-1 considered that the chemical
composition of a pozzolanic material, should contain at least 25%
by weight, of reactive silicon dioxide. The NF P18 513 standard
has limited, for Metakaolin, the minimal amount of these compo-
nents at 90% by mass. However and according to ASTM C 618,
the sum of SiO2 + Al2O3 + Fe2O3 should exceed 70% by mass
(Table 1). That’s what Changling [22] has investigated for some
clays. He has found that the sepiolite, having the lowest amount
of these components and which did not satisfy this requirement,
has recorded the lowest strength and pozzolanic activity. Similarly,
the smaller particle size of artificial pozzolans [39] with a higher
surface area and glassy phase content also improved the poz-
zolanic reaction [40]. On the other hand, some other physical
requirements were described by ASTM C 618. One such example
is the index activity, where the pozzolan cement strengths should
at least attain 75% of those obtained by the control cement at 7 and
28 days.
To summarize clays, clay wastes (CW) and clay wastes origi-
nally treated (CWIT) used in the development of artificial pozzolan
must satisfy some requirements. They should contain a minimum
of amorphous silica and alumina, to ensure the chemical reactivity.
Moreover, and in order to improve their chemical and physical
effects, those materials must be at least the same fineness as Port-
land cement.
2.2. Treatment
At the raw (crystalline) state, clays have no pozzolanic activity,
to acquire it, they should be treated. Whatsoever a mechanical
treatment [8] or thermal one [4,13], it must ensure a maximum
of material dehydroxylation. Thermal treatment is the procedure
allowing the transition of clay from a purely crystalline phase to
a state, most to least amorphous. It consists in bringing the mate-
rial under the effect of a thermal cycle up to desired temperature.
Typically, when heated, clays exhibit the following behavior:
Table 1
Some required properties for artificial pozzolans according to ASTM C 618.
Chemical and physical requirements ASTM C
618
Silicon dioxide SiO2 + aluminum oxide Al2O3 + iron oxide Fe2O3: 70
min (%)
Sulfur trioxide SO3: max (%) 4
Moisture content: max (%) 3
Loss on ignition: max (%) 10
Amount retained when wet-sieved on 45 lm (N° 325) sieve: 34
max (%)
Strength activity index with OPC at 7 days: min (% of control) 75
Strength activity index with OPC at 28 days: min (% of control) 75
Water requirement: max (% of control) 115
Autoclave expansion or contraction: max (%) 0.8
 S. Mohammed / Construction and Building Materials 140 (2017) 10–19

Dehydration: it occurs between 20 and 200 °C, and concerns the
free water removal. On the thermal analyzes curves, the dehy-
dration corresponds to an endothermic peak (DTA and DSC
curves) followed by mass loss (TG spectra).

Dehydroxylation: it is the most important phenomenon in the
clay calcination. It consists in the chemically bound water evap-
oration, from OH groups that contain the clay phyllite minerals.
In the temperature range beyond of 500 °C, the dehydroxylation
results an endothermic peak and a mass loss [41] (Fig. 2), which
vary from clay to another (Table 2).

Decarbonation: it concerns the passive phases of the clay (cal-
cite, dolomite, etc.). The decarbonation corresponds to releasing
CO2 upon transformation of these carbonates between 700 and
900 °C.

Recrystallization: it is an exothermic transformation, without
mass loss, resulting a rearrangement in the material. It must
be noted that the clay’s recrystallization, which happen above
900 °C, may lead to a drop in the pozzolanic reactivity.
The elaboration of an APC depends mainly on the material
dehydroxylation. Although the particle size of the treated sample
Fig. 2. TG-DTA analyzes of Bihar Muscovite.
Table 2
Optimal heat treatment of some phyllite clay minerals.
Phyllite minerals

Illite:
(K, H3O)(Al, MG, Fe)2 (Si, Al)4 O10[(OH)2, (H2O)] ? 3,5
H2O" + (K)(Al, MG, Fe)2 (Si, Al)4 O10,5

Montmorillonite:
(Na, Ca)0.3 (Al, Mg)2 Si4 O10(OH)2 nH2O ? (n + 1)H2O"
+ (Na, Ca)0.3 (Al, Mg)2 Si4 O11

Sepiolite:
Mg4 Si6 O15(OH)26H2O ? 7H2O" + Mg4 Si6 O16

Smectite:
(K, Ca)(Si4, Al)O10 (Al, Mg, Fe, Ti)(OH)2 ? H2O" + (K, Ca)
(Si4, Al)O11 (Al, Mg, Fe, Ti)

Muscovite:
K Al2 (Si3 Al) O10 (OH) 2 ? H2O" + KAl2 (Si3 Al)O11

Bentonite:

Chlorite
(Fe, Mg, Al)6 (Si, Al)4 O10 (OH)8 ? 4H2O" + (Fe, Mg, Al)6 (Si,
Al)4 O14
13
must be small as possible, allowing the temperature to reach the
material bottom, the thermal cycle must be well chosen. According
to the literature of artificial pozzolans, dehydroxylation depends
on many factors, such as:

The treatment temperature: it varies from a phyllosilicate to
another. The optimal temperature is that one which ensures
for the sample, a total dehydroxylation [4,13,42].

The holding time: it presents the duration that the sample
should be kept under the target temperature. The holding time
may be a determining factor against the pozzolanic character of
treated clay [4,13–15,43,44].

The heating rate: it may be crucial, that the rise in temperature
should be as low as possible to ensure the distribution and the
uniformity of temperature inside the sample [26].
Contrary to what has preceded, the elaboration of an APCW is
more difficult. This is due to the mineralogical variety that can
include these clay wastes. The optimum temperature for one clay
mineral may cause recrystallization to another mineral or decom-
position of some passive phases such as carbonates. So it seems
complicated to ensure, simultaneously, total dehydroxylation of
all phyllite minerals contained in these wastes. For clay wastes ini-
tially treated (CWIT), pozzolanicity of these materials is not guar-
anteed, because their calculation has not necessarily led to total
dehydroxylation.
2.3. Mechanisms of pozzolanic reactions
The main reactions of Portland cement hydration transform the
tricalcium silicate (C3S) and the dicalcium silicates (C2S) to Calcium
Silicate Hydrates (C-S-H) and Calcium Hydroxide (CH) (reactions
(1) and (2)). It is well known that the cement matrix acquires its
mechanical properties from C-S-H, which are the major part of
cement hydration. However, the liberated CH does not make a sig-
nificant contribution to strength and can be harmful to concrete
durability [56]. Pozzolanic materials have the opportunity to fix
this CH and produce Supplementary Cementitious Compounds
(SCC).
In the presence of water, Portlandite reacts with the added poz-
zolan resulting in additional calcium silicate hydrates (C-S-H), cal-
cium aluminates hydrates (CAH) and calcium aluminosilicate
Optimal heat hydrates (CASH) (reaction (3)). These reactions depend upon the
treatment level and the reactivity of pozzolan, which in turn depends upon
700 °C [21,45] the treatment conditions, the material purity and its fineness.
715 °C [46]
800 °C [47] C3S þ H ! C  S  H þ CH ðreaction1Þ
850 °C [17]
900 °C [18,19]
930 °C [48] C2 S þ H ! C  S  H þ CH ðreaction2Þ
800 °C [17]
800 °C [47]
830 °C [48] Pozzolan þ CH þ H ! SCCðC  S  H; CAH; CASHÞ ðreaction3Þ
800 °C [49]
810 °C [50]
830 °C [24]
750 °C [51]
3. Effects of artificial pozzolans on mortar and concrete
900 °C [19] properties
930 °C [48]
950 °C [18] Like all other traditional pozzolans (natural pozzolan, MK, SF,
700 °C [21]
FA, etc.), artificial pozzolans, developed from clays, CW and CWIT,
850 °C [37]
1000 °C [52] may significantly affect pastes, mortars and concretes properties.
700–950 °C [20] Although these pozzolans are less reactive, compared to some
720 °C [53] other materials such as MK and FA, their effects have been studied
750 °C [54]
for cement or clinker substitution rates between 10 and 20%
700 °C [55]
800 °C [23]
[25,26,37,48], and even up to 30% substitution for some others
[16,17,24]. The use of these pozzolans, in blended cements, influ-
ences on several cementitious properties in the fresh state as well
14 S. Mohammed / Construction and Building Materials 140 (2017) 10–19
as the hardened one: workability, hydration kinetic, mechanical
response, durability, etc.
Fresh properties of mortars containing 10% of dam’s sludge,
based on Kaolin and Illite/Muscovite minerals and heat treated at
different temperatures, were reported by Chikouche [26] (Table 3).
The water requirement was measured for normalized pastes based
on cements containing 10% of sludges treated for 5 h at 600 °C,
700 °C and 800 °C, with a heating rate of 10 °C/h. According to
the authors, the water quantity increases as the activation temper-
ature increase, which was explained by the higher fineness of the
blended cements by comparison to that of CEMI. As the addition
was finer than the cement (7000–3800 cm2/g), the fineness
increase provided a greater cement particles surface to be wetted.
Similarly, the increase of setting time has been attributed to the
fineness and the W/C ration increase.
Clays of Ca-Montmorillonite, Na-Montmorillonite, mixed layer
(Mica/Smectite), Illite and Sepiolite, heat treated at optimum tem-
peratures and used at 30% as a cement substitution in cement mor-
tars, were subjected to 28 days compressive strength tests by
Changling [22]. According to the authors results, while mortars
with Illite and Sepiolite had reached only 79 and 84% of the refer-
ence mortar strength, the other clays had allowed to an increase
between 113 and 125% compared with the reference mortar.
Ground waste clay bricks and heat treated clay were used by O’Far-
rell [32] in cement mortars. They reported that using these mate-
rials up to 20% of substitution and at 90 days, the strengths are
the same as or are greater than the control mortar. Similar findings
with strength enhancement can be pulled from the works of sev-
eral researchers [20,37,48].
Likewise, the effect of (APC), (APCW) and (APCWIT) on the fresh
and hardened properties of concrete has been widely studied in
recent years. In a previous study [57], we have demonstrated that
artificial pozzolan, obtained from heat treated clay and despite its
undesirable effect on the workability, may lead to concrete with
mechanical properties slightly less than those obtained for the con-
trol one. Heikal et al. [58] have shown that the use of (APCWIT),
obtained from ground clay bricks (GCBs), enhanced the compres-
sive strength of self compacting concrete. They attributed this
enhancement to the pozzolanic reaction leading to additional C-
S-H, which precipitated in some open pores. Similar results were
reported by Filho et al. [37], contrary to [59] where a decrease of
9% in the concrete compressive strength was found when 10% of
cement is replaced by GCBs. This study showed also that the GCBs
have caused an increase in porosity and water absorption, while a
slight decrease in the concrete slump and its thermal conductivity,
was obtained. Moreover, several studies are interested by the
advantages brought from incorporating MK in concrete. The use
of this (APC) in concrete improves significantly its compressive
strength [60,61,10] and reduces its permeability [61]. It has a pos-
itive impact on pore refinement and interfacial transition zone
(ITZ) enhancement of concrete, especially at later curing stages
[62].
In terms of durability, these materials have the advantage of
improving, mainly, the penetrability resistance of mortars and con-
cretes, through their filer and pozzolanic effects. Zhi et al. [59],
reported that the concrete made with (APCWIT) of GCBs had low
Table 3
Fresh properties of normalized pastes and mortars [26].
CEM I
Water requirement to obtain standard 133
consistency (cm3/500 g of cement)
±5
Setting time (mn) Initial 100
Final 210±4
chloride ion penetrability and high freezing–thawing resistance,
similar to what Filho et al. [37] have recorded. According to the
authors, this behavior may be associated with pore refinement pro-
moted by the replacement material that created difficulties to the
ionic transport inside mortars. They have shown also, that the use
of GCBs reduced the tensile strength loss of the control mortars
exposed to a 5% magnesium sulfate solution at the age of 200 days.
For (APC), and according to Gurber et al. [63], the use of 8% and
10% of MK significantly lowered the chloride ion diffusion coeffi-
cient of concrete. The same findings are reported by several studies
[30,61,64]. To summarize, the Table 4 provides a bibliographic syn-
thesis of the effects of inclusion, as partial cement replacement in
mortar and concrete, some (APC), (APCW) and (APCWIT).
4. Test methods
The evaluation of clays, CW and CWIT pozzolanicity may be car-
ried out using different chemical, physical and mechanical meth-
ods. These methods are on the basis of determining of the Ca
(OH)2 consumption by the reactive components of pozzolanic
materials.
4.1. Chemical tests
The chemical tests are direct methods from which pozzolanic
activity of clays, CW and CWIT may be assessed through the ability
of their amorphous phases to react with the lime. Foremost, it
should be recalled that the content of reactive SiO2 and Al2O3 in
the material must satisfy the chemical requirements mentioned
above. This amount may be easily determined by using the EN
196-2 standard. The most used chemical tests are:
4.1.1. Frattini tests
According to Donatello [79], the Frattini test is a commonly
used direct method that involves chemical titration to determine
the dissolved Ca2+ and OH concentrations in a solution containing
CEM I and the test pozzolan. Recently, it has been used to assess
the pozzolanicity of brick wastes [80], natural and treated Andesite
[38], montmorillonite [81] natural pozzolans [82], Metakaolin [9],
porcelain and marble industrial waste [39]. According to its
description in the EN 196-5 standard, the Frattini test consists to
make into reacting 20 g of test samples prepared by mixing 80%
of CEM I and 20% of pozzolan in 100 ml of deionized water. The
pozzolan must be finely ground (none retained on the 125 mm
sieve). The mixtures should be kept in a sealed plastic bottle at
40 °C for at least 8 days. For each test time (8, 28, 90 days, etc.),
samples will be vacuum filtered and the filtrate will be analyzed
for Ca2+ and OH. Results will be as a curve, in which the Ca2+,
expressed as equivalent CaO in mmol.l1, is linked to OH- in
mmol.l1. The [CaO] concentration can be calculated using the for-
mula given in the above standard to trace the curve of lime solubil-
ity (Fig. 3): [CaO] = 350/([OH]-15). Only results lying below the
curve (zone 1) are indicative of pozzolanic activity, which corre-
sponds to the removal of Ca2+ from the sample.
MC600/10 MC700/10 MC800/10
137 142 144
±5 ±4
165 180 185±4
260±6 260±6 270±6
 S. Mohammed / Construction and Building Materials 140 (2017) 10–19 15

Table 4
Some effects of using (APC), (APCW) and (APCWIT) as partial cement replacement in mortar and concrete.

APC
Metakaolin Other calcined clay
Compressive strength Mortar SF ˃ MK ˃ Contr ˃ FA [65] +2.38 (treated clay) [57]
Concrete +24.1% [61] 2.29% (treated clay) [57]
Setting time +5% [66] 11.1% (treated Diatomite) [70]
Water demand +0.33% [66] +31.69% (treated Diatomite) [70]
Workability (slump) 82.35% [67] Contr ˃ (treated Illite) [17]
Heat of hydration Contr ˂ MK ˂ SF [68] Contr ˃ Activated Hwangtoh clay [71]
Dynamic elastic modulus FA ˂ Contr ˂ MK ˂ SF [65] Contr ˂ Sepiolite [72]
Porosity +55.6% [10] +21.21% (treated Illite) [16]
Water absorption +18.99% [69] /
Chloride ion penetration 88.81% [63] /
Freeze – Thaw resistance SF ˃ MK ˃ FA ˃ Contr [65] Contr ˃ Treated clay [73]
APCW APCWIT
Compressive strength Mortar +1.82% (Dum sludge) [27] +10.59% (GCBs) [32]
Concrete Contr ˂ Paper sludge [74] 4.5% (GCBs) [59]
Setting time Contr ˂ Sewage sludge [75] 16.67% GCBs [76]
Water demand Contr ˂ Sewage sludge [75] +3.64% GCBs [76]
Workability (slump) Contr ˃ Paper sludge [74] Contr ˃ Ceramic waste [77]
Heat of hydration Contr ˂ Dum sludge [26] Contr ˃ Ceramic waste [78]
Dynamic elastic modulus / Contr ˂ GCBs [37]
Porosity +13.67 (Paper sludge) [29] Contr ˂ GCBs [30]
Water absorption Contr ˂ Paper sludge [74] +12.38% (GCBs) [59]
Chloride ion penetration / 84.35% (GCBs) [30]
Freeze – Thaw resistance Very good resistance (Paper sludge) [29] High resistance (GCBs) [59]

(Contr) Denotes the control mortar or concrete.

GCBs: ground clay bricks.
(+) Denotes an ‘‘increase” in the metric was reported.
() Denotes a ‘‘decrease” in the metric was reported.

4.1.2. Saturated lime test
Contrary to the previous test, in this one, the pozzolan to be
tested is mixed with saturated Ca(OH)2 solution instead of CEM I
and water. This lime solution may be prepared by dissolving 2 g
of hydrated lime in 1 L of deionized water. The saturated lime test,
which is considered as a simplified and non standardized version
of the Frattini test, involves in reacting 75 ml of this solution with
1 g of the studied pozzolan. Similarly, samples must be kept in a
sealed plastic bottles at 40 °C until the desired curing time. The
amount of lime fixed by the pozzolan will be determined by mea-
suring the residual dissolved calcium [38,79,81].
It should be noted that the French standard NF P18-513
describes a shorter version of the saturated lime test and known
as Chapelle test modified. By using this chemical method, mea-
surement of the fixed quantity of Ca(OH)2 on pozzolan materials
allows to assess their pozzolanic activity. For doing, 1 g of pozzolan
is reacted with a solution prepared by dissolving 2 g of CaO in
250 ml of deionized water, during 16 h at 90 °C. The non reacted

Fig. 3. The Frattini test results (EN 196-5).

16 S. Mohammed / Construction and Building Materials 140 (2017) 10–19
lime is then measured and the result will be expressed in mg of Ca
(OH)2 fixed by g of pozzolan [83].
4.2. Physical methods
The use of artificial pozzolans affects substantially the charac-
teristics of cement matrix, during hydration and after curing, and
the growth of residual hydrates especially: Portlandite, C-S-H,
CAH, and CASH. This influence varies from pozzolan to another
and mainly depends on the reactivity of the used material. Physi-
cally, the reactivity of such pozzolan is calculable by continuous
assessment of the Portlandite amount in the cement matrix (com-
pared to that of reference). Pozzolanic activity means a decrease in
the Portlandite quantity against an increase of the matrix content
from C-S-H, CAH, CASH. Recent studies have shown that it is pos-
sible to quantify the Portlandite content, through the mass loss
assessment between 400 and 600 °C, using the thermogravimetric
analysis [72,81,84]. Moreover, Paya et al. [85] showed that we can
easily calculate the fixed lime percentage, using the relationship:
 
½CHC  C %   CHP
Fixed Lime ð%Þ ¼ 100
CHC  C %
where CHC, CHP are, respectively, the CH amounts in control and
pozzolan pastes, measured from curves of TG analysis in the corre-
sponding temperature range, and C% is the proportion of cement in
the pastes. The study showed that a reactive material can fix up to
86% CH. However, a very active pozzolana may lead to a CH level, in
the matrix, near to zero, according to Tironi et al. [84] (Fig. 4). The
pozzolanic activity assessment should be done also through XRD
(Fig. 5) [61,86], or calorimetry [87]. Other physical methods such
us NMR and IRTF can also be useful, but recourse to such methods
remains very limited.
4.3. Mechanical tests
The consumption of Portlandite, by pozzolanic materials, gives
rise to SCC, which increases, usually late, the mechanical behavior
of mortars and concretes. One of the most efficient methods for
evaluating the reactivity of these artificial pozzolans is the com-
pressive strength activity index. To conduct this test, there are no
specifications for the confection of mortar specimens. The control
OPC
Fig. 4. Use of XRD to assess the CH amount at 7 days for cement pastes without and with 15% of Metakaolin.
mortar should be prepared with 100% of a given Portland cement.
While test samples must be prepared in the same manner, except
that selected percentages of the cement will be replaced with the
test pozzolans. Commonly and according to the ASTM C618, the
cement substitution rate is 20% by weight [79], but other percent-
ages can be also considered, such as 10%, 40% [39], 30% [81] or 15%,
according to the NF P18-513. The pozzolanic activity index
increases with time, so the curing time may be crucial for this test.
Depending on the studied pozzolan reactivity, we may assess the
strength activity index (SAI) of the samples, for 7 or 28 days, by
using the following equation:
SAIðtÞ ¼ 100 ðRi=RcÞ; where :
- SAI(t): The strength activity index at (t) days.
- Ri: The compressive strength of the test mixture at (t) days.
- Rc: The compressive strength of the control mixture at (t) days.
Whatever the substitution rate and the curing time, the mate-
rial will be considered as pozzolanic if at least, the strength activity
index is 75%. The same formula has been used by Patel et al. [39]
and Tahsien et al. [88], according to ASTM C311-11, to evaluate
the SAI of circulating fluidized bed combustion (CFBC) fly ash.
Moreover, ASTM C593-06 offers the possibility to assess the poz-
zolanic reactivity at elevated temperatures. We note here that
the obtained strength improvements exhibit a physical (fineness)
and chemical (reactivity) effects of the studied pozzolan, contrary
to the above tests, where only the chemical reaction of the material
with lime was considered.
The reactivity of these artificial pozzolans may also improve
some mortar and concrete properties, such as: porosity, absorp-
tion, freeze and thaw resistance, durability, etc. The monitoring
of these mechanical properties may likewise allow to determine
the reactivity of such pozzolan, but less pertinently.
4.4. Comparison between tests of pozzolanicity
Tests of Frattini, SL and SAI, cited above, allow to investigate the
pozzolanic activity of Clays, CW and CWIT in different ways.
Although it is recommended during this evaluation to carry out
at least one test allowing the evaluation of Portlandite consump-
tion over time [79], this variety of tests does not guarantee, in most
OPC + 15 % MK
 S. Mohammed / Construction and Building Materials 140 (2017) 10–19
Fig. 5. Use of DTA methods to assess the pozzolan effect on CH amount.
cases, alike results. A such material may have different values of
pozzolanic activity from a test to another. Based on their
researches on some artificial pozzolans, Donatello et al. [79] had
effected a comparison between these different methods of poz-
zolanicity assessment. They reported that for an objective compar-
ison, tests difference in terms of curing time, test temperature and
lime: pozzolan ratio, as mentioned in Table 5, must be taken into
consideration. The study showed that a significant correlation
between tests of Frattini and SAI has been found. However, there
was no correlation between these tests and the SL one. Since the
Portland cement, when fully hydrated, may convert about a quar-
ter of its initial weight to Portlandite [56], the authors had attrib-
uted this convergence mainly to the mass ratio of Ca(OH)2 to
pozzolan which was 1:1 in both tests, whereas it was 0.15:1 in
the SL case.
According to the researchers [79], MK showed the highest activ-
ity. Its ability to remove a high level of Portlandite, according to the
Frattini test results, has allowed to strength improvement (SAI) by
forming additional C-S-H phases, hence the correlation between
both tests. Pozzolanic activities of MK, SF and FA given by the SL
test after 7 days were high (90%) and identical, while these mate-
rial activities were 94.4%, 33.1% and 50.7% respectively according
to the Frattini test.
Besides the difference between these results, the non-
correlation between Frattini test and the SL one, was more obvious
for incinerator sewage sludge ash (ISSA), where a negative poz-
zolanic activity has been found from the Frattini test, whereas,
the SL method showed a positive result. The authors attributed this
finding to the lack of Ca(OH)2 in the SL test (6.67 times less). Thus,
Table 5
Comparison between tests of: Frattini, SL and SAI [79].
Frattini Test SL test
Curing time (days) 8 Not specified
Test temperature 40 °C 40 °C
Lime: Pozzolan ration 1:1 0.15:1
17
they suppose that the reduction of pozzolan level could allow to
similar result as the Frattini test.
Except MK, the comparison of SAI test with SL one showed that
no correlation existed between all material activities obtained
from both methods. In addition to the procedures difference
(chemical for SL and physico-mechanical for SAI), the authors gave
two reasons for this results divergence. The SAI results are affected
by the w/c ration. Increase in water requirement of pozzolans,
must lead to water excess, which may induce to an increase in
matrix porosity and a decrease of its strength. While the SL results,
are mainly affected by the test temperature and the accuracy of
measurements.
In the case of physical methods, especially that based on ther-
mal analyses (TG-TDA, DSC), the major drawback is the difficulty
of determining the hydrates border temperatures. Although the
mass loss due to Portlandite is usually sought in the temperature
range between 400 and 600 °C [89], the border temperatures of
other hydrates (C-S-H, CAH and CASH) are difficult to determine
and vary from author to another. For the XRD, the pozzolanic activ-
ity assessment proves to be very complicated, since this technique
allows the detection of only crystalline phases.
5. Conclusion
Based on the discussed points, the following conclusions can be
drawn:
- Clays, clays wastes and clay wastes initially treated can lead to
artificial pozzolans.
- In all of these materials, phyllite minerals are at the origin of
this pozzolanicity.
- To elaborate an APC, the raw material must be treated to ensure
its total dehydroxylation. Furthermore, three factors affect its
reactivity: its (SiO2 + Al2O3 + Fe2O3) content, its dehydroxyla-
SAI tion (amorphousness) degree, the fineness of its particles.
28 - Mineralogical variety and therefore the different thermal
23 °C behaviors, make very difficult to define the optimal treatment
1:1 that allowing to elaborate an APCW.
18 S. Mohammed / Construction and Building Materials 140 (2017) 10–19
- In the APCWIT elaboration, the major problem is the initial
treatment which cannot guarantee a total dehydroxylation
without recrystallization of the material.
- Like all artificial pozzolans, those above, despite their weak
reactivity, may lead to improvements in mortars and concretes,
whether in the fresh state or the hardened one.
- The pozzolanicity assessment may be carried out using differ-
ent methods. The chemical tests, in particular the Frattini test,
give an accurate estimation of the material capacity to consume
lime. The physical tests allow to follow approximately the con-
sumed Portlandite rate over time. However, mechanical method
is the least efficient because it takes into account both poz-
zolanities: chemical (reactivity) and physical (fineness).
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