Construction and Building Materials 211 (2019) 814–823

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Construction and Building Materials

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Effect of thermal treatment on pozzolanic activity of excavated waste

clays
Hernan Yanguatin a,c,⇑, Jose H. Ramírez a, Alejandra Tironi b, Jorge I. Tobón c
a
Grupo de investigación en Materiales, Catálisis y Medio Ambiente, Facultad de Ingeniería, Universidad Nacional de Colombia, Carrera 45 # 26-85, 111321 Bogotá, D.C, Colombia
b
Facultad de Ingeniería, CIFICEN (CONICET-CICPBA-UNCPBA), Av. del Valle 5737, Olavarría, Argentina
c
Grupo del Cemento y Materiales de Construcción (CEMATCO), Materials and Minerals Department, Faculty of Mines, Universidad Nacional de Colombia, Colombia

h i g h l i g h t s

 Amorphous phase of calcined excavated clays affects their particle size distribution.
 Calcined excavated clays at 650 °C show pozzolanic activity at 7 days.
 Effect of calcination temperature on the compressive strength is statistically significant.
 Calcined excavated clays can be used as supplementary cementitious materials.

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

Article history: Samples of excavated waste clays were characterized by X-ray fluorescence, laser granulometry, specific
Received 24 October 2018 surface area, X-ray diffraction, and thermo-gravimetric analysis. Excavated clays were calcined at 550 °C
Received in revised form 26 February 2019 and 650 °C in order to investigate their potential pozzolanic activity. The effect of thermal activation also
Accepted 25 March 2019
was determined by factorial experiments with two factors in randomized complete blocks. Pozzolanic
activity was evaluated by calcium hydroxide fixation, the Frattini test and the compressive strength at
7 and 28 days. The results indicate that calcined excavated clays at 650 °C presented pozzolanic activity
Keywords:
at 7 days and showed an increase percentage of compressive strength on average 13%.
Excavated waste clays
Calcined excavated clays
Ó 2019 Published by Elsevier Ltd.
Kaolinite
Pozzolans
Calcium hydroxide fixation
Frattini test
Increase percentage of compressive strength

1. Introduction The potential use of those excavated clays as a supplementary

Construction and demolition waste (CDW) from local
infrastructure projects are composed mainly by materials such as
concrete, ceramics, asphalt, wood, paper, glass and excavated soil.
Depending on local geological conditions and anthropogenic activ-
ities, excavated material can be organic material, rocks, gravel,
sand and clays [1]. For example, in the main cities of Colombia in
2011, were produced 22 million tonnes of CDW, meanwhile in
Bogota city in 2012, were produced about 13 millions of tonnes;
which around 73% corresponded to excavated clays [2]. In this
case, the only management alternative for these wastes had been
their disposition at landfill, with impacts associated on the
landscape, the soil and the water.
⇑ Corresponding author.
E-mail address: hyanguatinb@unal.edu.co (H. Yanguatin).
cementitious material (SCM) is attracting considerable interest,
because their mineralogical composition is related with clay min-
erals (kaolinite, illite and montmorillonite) and impurities such
as quartz and feldspar [3]. Then could be possible activate them
with thermal treatments in order to remove their structural water,
through a process of dehydroxilation in order to obtain a material
with pozzolanic activity, that it can be used as partial substitute of
the clinker [4,5].
The thermal activation of clays produces a state of structural
disorder that is a metastable state, therefore metakaolin refers to
the kaolinite that has been calcined and it shows an amorphous
reactive structure [6–11]. This pozzolanic activity depends on the
dehydroxylation degree and the available surface for reaction,
which are affected by calcination conditions (residence time, tem-
perature and heating regime) [12]. The calcium hydroxide quantity
that will react producing a cementing compound like C-S-H and

https://doi.org/10.1016/j.conbuildmat.2019.03.300
0950-0618/Ó 2019 Published by Elsevier Ltd.
 H. Yanguatin et al. / Construction and Building Materials 211 (2019) 814–823
some alumina-hydrated phases, depend on the nature, the quality
and the quantity of active phases in calcined clays; meanwhile the
reaction speed depend of the specific surface area, the water/solid
ratio and the curing temperature [13].
The calcined clay reactivity evaluated by methods based on
portlandite consumption usually does not correlate well with com-
pressive strength, therefore have been introduced methods to
determine the chemical reactivity by measurement of the heat
release during reaction using isothermal calorimetry and by bound
water determination [14–17].
Recent developments in the characterization of excavated clays
have established their chemical and mineralogical composition,
particle size distribution and specific surface area [3,18–20]. Zhou
et al. [3] found kaolinite, illite and montmorillonite in a London
excavated clay, that was calcined at 600 °C, 700 °C, 800 °C, 900 °C
and 1000 °C during two hours. The kaolinite dehydroxilation hap-
pened between 350 °C and 600 °C, while the montmorillonite and
illite dehydroxylation took place between 600 °C and 950 °C [3].
The pozzolanic activity was evaluated using Frattini test, calcium
hydroxide consumption test and strength activity index (SAI).
According to Frattini test results, the calcined excavated waste
clays at 800 °C, 900 °C and 1000 °C showed activity after 8 and
15 days of cured, as well as higher percentages of consumption
of calcium hydroxide. The SAI at 28 days was greater than 0.75
for calcined clays between 700 °C and 1000 °C.
Du and Pang [20] collected from a construction site at Singapore
a Marine clay, with an kaolinite content approximate of 20% which
was calcined at 600 °C, 700 °C and 800 °C. The pozzolanic reaction
for calcined marine clay was evaluated through the cumulative
heat released, calcium hydroxide consumption and compressive
strength of mortar. Despite the low kaolinite content, mortar with
marine clay calcined at 600 °C exhibited a high strength activity
index of approximately 0.9.
It was concluded that excavated waste clays can be transformed
into SCM when they are calcined between 600 °C and 900 °C and
their pozzolanic activity depend on kind and quantity of clay min-
erals, impurities and calcination conditions [3,20].
The recent studies on kaolins, kaolinitic clays and commercial
kaolins point out that their thermal activation develops pozzolanic
activity and it allows use them like SCM; meanwhile, still have to
be established the effect of thermal treatments on both the charac-
teristics and the pozzolanic activity of excavated waste clays.
In that regard, the aim of this study is to evaluate the potential
use as SCM of excavated Colombian clays, determining the signifi-
cant effect of thermal activation on their characteristics and their
pozzolanic activity.
In this work, five samples of excavated waste clays were chem-
ically, physically and mineralogically characterized and thermally
activated using two calcination temperatures and two residence
times. The pozzolanic activity of each calcined clay was evaluated
in lime pastes and mortars blended with 20% by mass replacement.
Table 1
Chemical composition of excavated waste clays and cement.
Parameters Sample
A1 A2 A3
SiO2 68.4 76.3 68.9
Al2O3 21.1 16.6 20.4
Fe2O3 5.1 2.7 6.2
CaO 1.5 0.5 0.5
Na2O 0.3 0.4 0.4
K2O 1.2 1.2 1.4
MgO 0.7 0.9 0.7
TiO2 0.9 0.9 0.9
SO3
LOI 6.1 3.4 5.7
815
2. Materials and methods
2.1. Raw materials and characterization techniques
Five samples (A1-A5) of 5 kg of excavated waste clays were selected from differ-
ent zones of the city according to Bogota geological information [21] and in accor-
dance with the purposive sampling of the biggest CDW generators. The excavated
clays were dried at room temperature and grinded in a ball mill for to pass them
through the 150 mm sieve (#100).
Clay particle size distribution was carried out in a Mastersizer 3000 with a dry
dispersion unit. The Blaine method was chosen in order to calculate the specific sur-
face area, according to ASTM C204 [22].
The chemical composition of the clays was obtained by X-ray fluorescence
(XRF) using a Philips MagixPro PW-2440 spectrometers with a rhodium X-ray tube,
the clays were mixed with Merck wax in the ratio 0.1 wax/sample, and pressed into
aluminum cups with a hydraulic press at 120 kN for 60 s. Results are shown in
Table 1.
Excavated clays mineralogical composition was identified by X-ray diffraction
(XRD) using a Panalytical X’pert PRO, with a 3° 60° (2h) range and 0.02 step and
with database COD_2016. The kaolinite content was quantified by the Rietveld
method with PANalytical Highscore Plus software and the results were validated
after with stoichiometric calculations [23] and by thermogravimetric analysis
(TGA) from the mass loss over the kaolinite dehydroxilation range [14]; these anal-
yses were performed in a Mettler Toledo analyzer with a nitrogen flow of 100 mL/
min and from 25 to 800 °C at a heating rate of 10 °C/min. FWHM – 001 index was
used to analyze the crystallinity of kaolinite.
On the other hand, the samples were coated with gold films for obtain scanning
electron micrographs, using a Microscope Tescan Vega 3 SB with a secondary elec-
trons detector, and applying an accelerating voltage of 8 kV.
2.2. Clays calcination
The excavated clays were oven dried at 100 °C for 24 h and then each one of
them were calcined at 550 °C, 650 °C and 750 °C for 1 and 3 h of residence time,
in a programmable laboratory furnace HE 487 using a fixed bed technique and cool-
ing at room temperature.
The analysis of variance of two factors (calcination temperature and residence
time) with BET specific surface area as response variable showed that the temper-
ature calcination had a significant effect and the Duncan test stated that the less
temperature, the higher BET area. For this reason, and considering that TGA is a
technique suitable to select the calcination temperature for complete kaolinite
dehydroxilation [24], the excavated clays were calcined at 550 °C for 1 h and
650 °C for 3 h, modelling a low and high power consumption scenario, respectively.
Calcined excavated clays were characterized using particle size distribution,
specific surface Blaine and XRD for check the kaolinite transformation.
2.3. Pozzolanic activity
Cement used for pozzolanic activity was a Portland cement kind A and B, whose
chemical composition is showed in Table 1. Cement kind A had an estimated Bogue
potential phase composition of 56% C3S, 19% C2S, 7% C3A and 11% C4AF by mass;
without additions. While cement kind B had an estimated of 64% C3S, 14% C2S, 3%
C3A and 13% C4AF by mass and limestone is added as minor component (5%).
Pozzolanic activity was assessed using the calcium hydroxide fixation test, Frat-
tini test, and compressive strength test. The calcium hydroxide fixation test was
done mixing 10 g of calcined excavated clay and 10 g of analytical grade Ca(OH)2
with 20 mL of distilled water in order to obtain pastes that were stored in plastic
vials at 40 °C for 14 and 28 curing days. Afterward the pastes were ground by hand
inhibiting the hydration process with acetone and removing its excess using a vac-
uum pump, then the samples were dried at 60 °C and passed through a #200 sieve.
TGA was done on the dried samples in a N2 atmosphere, from room temperature up
Cement
A4 A5 A B
68.3 70.2 19.2 20.1
20.3 18.4 4.4 3.6
5.6 5.0 4.1 3.9
1.6 2.3 65.2 64.2
0.4 0.3 0.3 0.1
1.3 1.2 0.4 1.1
0.8 0.7 0.7 0.8
0.7 0.8
5.2 2.8
9.4 7.3 1.9 3.1
816 H. Yanguatin et al. / Construction and Building Materials 211 (2019) 814–823

to 800 °C at a heating rate of 10 °C/min. The percentage of fixated calcium hydrox-
ide was calculated, taking as reference the initial amount of Ca(OH)2 in each sample
as described by Mendoza & Tobón [25].
In the Frattini test, according to British Standard BS EN 196-5, 20 g of test sam-
ple consisting of 80% of Portland cement kind B and 20% by mass of calcined clay
mixed with 100 mL of boiled distilled water. After preparation, samples were left
for 2, 7 and 28 days in a sealed plastic container at 40 °C. At test time, samples were
vacuum filtered through paper and cooled at room temperature in sealed Buchner
funnels. The amount of Ca2+ and OH– in the water of contact with the tested sam-
ples stored is compared with the solubility curve for Ca(OH)2 in an alkaline solution
at the same temperature, then when the [Ca2+] and [OH–] determined in solution is
located below the solubility isotherm indicates that calcium hydroxide is consumed
and the calcined clay is considered pozzolanic.
Compressive strength test was assessed on control mortars with Portland
cement kind A:standard Ottawa sand ratio of 1:2.75 and water/cement ratio of
0.485. Blended mortars were made by replacing the Portland cement with 20% cal-
cined excavated clays and a water/cementing material ratio necessary for obtain a
flow of 110 ± 5, according to ASTM C 109 [26]. The mortars were cured in a moist
cabinet and mold release after 24 h for immersed them in water saturated with
lime until test age. Compressive strength at 7 and 28 days was determined in a uni-
versal testing machine Shimadzu AGS-X 250 kN as the average of three replicates of
mortar samples.
To study the thermal treatment effect on the pozzolanic activity of samples
blended with calcined clays, was established an experiment design of two factors
in randomized complete blocks. Each kind of excavated clay was considered as a
block and the two factors were the calcination temperature and the hydration
age. R statistical software was used for the regression analysis of the experimental
data obtained.
3. Results
3.1. Characterization of raw and calcined clays
The chemical composition of five excavated waste clays and
two kinds of cement is shown in Table 1. The major oxides are rep-
resented by SiO2, Al2O3 and Fe2O3 in total content higher than 70%

Table 2
Physical properties of excavated clays and calcined excavated clays.

Temperature Property A1 A2 A3 A4 A5
Raw d10 (lm) 1.98 2.14 1.54 2.81 2.15
d50 (lm) 12.15 11.28 8.55 19.05 16.07
d90 (lm) 119.23 37.77 122.81 129.56 116.35
Blaine (cm2/g) 8769 4670 5166 5855 5620
550 °C d10 (lm) 2.06 2.07 1.68 2.53 1.95
d50 (lm) 14.77 11.41 15.54 17.64 14.13
d90 (lm) 105.2 38.02 292.62 133.7 103.41
Blaine (cm2/g) 8049 5978 6909 6453 6719
650 °C d10 (lm) 1.97 2.02 1.59 2.53 2.01
d50 (lm) 17.63 12.33 17.11 19.92 18.24
d90 (lm) 132.4 38.99 265.42 129.22 107.37
Blaine (cm2/g) 5128 4918 5312 5624 5308

6 6
A1 A2
5 5
Volume ( %)
Volume (%)

4 550°C 550°C
4
3 650°C 3 650°C
2 2
1 1
0 0
0.1 1 10 100 1000 0.1 10.0 1000.0
Parcle size (μm) Parcle size (μm)

6 6
5 A3 5 A4
Volume (%)
Volume (%)

4 550°C 550°C
4
650°C 650°C
3 3
2 2
1 1
0 0
0.1 10.0 1000.0 0.1 10.0 1000.0
Parcle size (μm) Parcle size (μm)

6 A5
5 550°C
Volume (%)

4 650°C
3
2
1
0
0.1 10.0 1000.0
Parcle size (μm)
Fig. 1. Particle size distribution of raw and calcined excavated clays.
 H. Yanguatin et al. / Construction and Building Materials 211 (2019) 814–823
and according with requirements of ASTM C 618 for Class N
pozzolans.
The silica contents were similar to those reported by Avet et al.
[14] and by Tironi et al. [27] for kaolinitic clays, who found per-
centages of 68.4% and 74.8% respectively.
Physical properties of excavated clays and calcined excavated
clays are summarized in Table 2. The specific surface areas Blaine
of raw excavated clays were between 4670 cm2/g and 8769 cm2/
g, while d50 were between 8.55 lm and 19.05 lm.
After calcination at 550 °C, the mean particle size of A1 clay
increased accompanied by a decrease in specific surface area
Blaine. A2 and A3 clays showed increases of both Blaine and d50,
these results were consistent with previous results reported by
Fabbri et al. [6], who point that the apparent contradiction can
be explained by considering that the dehydroxylated particles tend
to aggregate, producing new porous grains with larger surface. The
reduction of d50 in A4 and A5 clays, it means that the effect con-
traction prevails on the aggregation effect. Calcination at 650 °C
of A1, A4 and A5 generated a reduction of the surface Blaine due
to increase of d50 when the aggregate particles start a sintering
process.
Particle size distribution of excavated clays is presented in
Fig. 1. A1, A5 and A3 raw clays show a trimodal distribution; the
finest fraction is in the range of 0.3–20 mm; the medium fraction
in the range of 20–100 mm and the coarsest is greater than
100 mm, with three maxima at about 5 mm, 45 mm and 450 mm,
respectively. The A2 and A4 raw clays both show a bimodal
Fig. 2. SEM micrographs of excavated clays before calcination: (a) A1 (b) A2 (c) A3 (d) A4 (e) A5.
817
distribution, with particle sizes between 0.4 mm and 300 mm for
A2 and between 0.5 mm and 1000 mm for A4.
Calcination of clays at 550 °C and 650 °C generates an amorphous
phase that affects the particle size distribution. The trimodal distri-
bution became bimodal with an increase of d10 and d50 and maxima
at about 11 mm and 45 mm, when the A1 clay was calcined at 550 °C.
The calcination at 550 °C of the A3 clay generates a rise of particles
volume with a diameter greater than 300 mm, generating increases
in d50 y d90; while for A5 clay it generates a rise of particles volume
with a diameter greater than 20 mm. Such increases were due to the
rise of temperature produces dehydroxylated kaolinite particles
that tend to aggregate and thus the particle size increases [6].
The calcination at 650 °C increases the d50 on average 27%,
while it reduces the specific surface Blaine just on average 12%, rel-
ative to the raw clays. This suggests that the significant rise of d50
is associated with the formation of a high amount of amorphous
phase that it involves agglomeration; this is consistent with the
results of Fabbri et al. [8] and Ilic et al. [28] for commercial kaolins
and kaolinitic clays.
On the other hand, the excavated clays morphological charac-
teristics are shown in Fig. 2 (a) – (e). It is observed a structure typ-
ical of the kaolinite crystals, pseudo hexagonal plates in small
flakes form with irregular edges and weakly aggregated.
The pseudo hexagonal shape is more defined for A1 clay that for
A3 clay, while the A5 clay has edges well defined in comparison
with A2 clay. The presence of some large particles in A2, A4 and
A5 was consistent with their particle size distributions.
818 H. Yanguatin et al. / Construction and Building Materials 211 (2019) 814–823
The calcination effect is related to the kaolinite plates damage,
the particle agglomeration and the irregular shapes with undefined
edges. These transformations are evident in Fig. 3(b) – (d) for A1
and A4 clays, calcined at 650 °C.
In relation to thermal behavior of excavated waste clays, ther-
mogravimetric analysis was conducted and shown in Fig. 4. The
total mass losses were between 4% and 11% at temperatures close
to 800 °C; meanwhile the highest losses (3% 8%) occurred
between 400 °C up to 650 °C, which confirms the dominance of
kaolinite dehydroxilation effect pointed by Alujas et al. [15].
The mass loss at temperatures less than 100 °C represents
removal of absorbed water on the particles surface, and between
100 °C and 400 °C is related to pre-dehydroxylation process as a
result of the octahedral layer reorganization [29].
Fig. 3. SEM micrographs of excavated clays: (a) A1 uncalcined (b) A1 calcined at
650 °C (c) A4 uncalcined (d) A4 calcined at 650 °C.
0 combined water relative to blended paste, calculated as the mass
-2
Mass loss (%)
-4
-6
-8
-10
-12
0 100 200 300 400 500 600 700 800
Temperature (°C)
Fig. 4. TG curves of excavated wasted clays.
Between 400 °C and 650 °C kaolinite dehydroxilation and meta-
kaolin formation take places and the mass loss over this range
shows the dehydroxylation of other clay minerals such as illite.
The differences in mass loss percentages among the excavated
clays are caused by the kaolinite contents various. The procedure
used to calculate the initial content of kaolinite is as described
by Avet et al. [14], from mass loss in the temperature range when
occurs the dehydroxylation.
The XRD patterns for bulk raw and calcined excavated clays are
shown in Fig. 5 (a-b). The clay minerals identified are kaolinite and
illite, as this is consistent with chemical composition by XRF, where
the presence of K2O could be associated to illite. The excavated clays
present very strong peaks of quartz, well-defined main peak of
kaolinite (2h = 12.34°) and a weak main peak of illite. The peaks rel-
ative to kaolinite disappear when the excavated clays are calcined
both at 550 °C and 650 °C (Fig. 5b), indicating that the dehydroxyla-
tion take place, while the appearance of a dome between
2h = 33 36° notes the transformation to an amorphous phase
[3,30].
The results of minerals content quantification of the excavated
clays validated by Rietveld quantitative X-ray diffraction, TGA
[14] and stoichiometric calculations [23] are reported in Table 3.
The A1 and A4 clays have the highest contents of kaolinite and
the lowest contents of quartz, they are consistent with chemical
composition because show the highest contents of Al2O3 (21.1%
and 20.3%) y lowest contents of SiO2 (68.4% y 68.3%); however
SiO2 can be also part of smectite or quartz, therefore, was necessary
supplement this analysis with thermogravimetric analysis and X-
ray diffraction.
The structure of excavated clays according to FWHM-001
kaolinite crystallinity index is ordered because their values are less
than 0.3.
3.2. Pozzolanic activity
The calcium hydroxide fixation percentage of the excavated cal-
cined clays (AC1 up to AC5) calculated from TGA is showed in
Fig. 6. Clays with the highest kaolinite contents (AC4, AC3 and
AC1) calcined at 650 °C fixed the highest percentages (around
40%) after 7 days of hydration, while clays with lowest kaolinite
contents just fixed around 30%.
After 28 days, the AC4 clay calcined at both 550 °C and 650 °C
fixed the highest percentages (40% and 50%, respectively), while
AC2 clay fixed just 32% and 38%. The excavated clays calcined at
650 °C are always more reactive than the clays calcined at
550 °C, their reactivity is on average 10% and 5% higher at 7
and 28 days, respectively. This behavior is associated with the
thermal treatments and the mineralogical composition, such that
the AC1 calcined at 550 °C shows the less reactivity at 7 days but
it improves at 28 days and even when is calcined at 650 °C. The
AC2 and AC5 calcined at both 550 °C and 650 °C and according
to their lower kaolinite content, present the less reactivity at
28 days.
The calcined clay reactivity also was assessed determining the
loss in the temperature range of 110–400 °C to determine approx-
A1
imately the amount of C-S-H, C-A-H and C-A-S-H phases [31,32].
A2
Fig. 7(a-b). shows the percentages corresponding to combined
A3
water relative to blended pastes with clays calcined at 550 °C
A4
and 650 °C.
A5
The combined water relative to blended paste showed rising
trend in whole samples due to the pozzolanic reaction that formed
reaction products like C-S-H and some alumina-hydrated phases.
Then, the amount of C-S-H, C-A-H and C-A-S-H phases in the
blended pastes with clays calcined at 650 °C is higher than in
pastes with clays calcined at 550 °C after 7 days of curing.
 H. Yanguatin et al. / Construction and Building Materials 211 (2019) 814–823 819

650°C-3h - - - Q
Q
550°C-1h ̶ ̶ ̶ ̶ ̶ ̶ ̶
Q I IQ Q Q
I K I K KQ Q
A5 A5
A4 A4
A3 A3
A2 A2
A1 A1

4 8 12 16 20 24 28 32 36 40
4 8 12 16 20 24 28 32 36 40
Posion (°2θ) Posion (°2θ)
a) b)
Fig. 5. XRD of raw (a) and (b) calcined excavated clays. K–kaolinite, I-illite; Q-quartz.

Table 3 Interaction between temperatures and curing time is also sta-

Mineralogical composition of excavated waste clays and FWHM-001 index.
tistically significant at 95% confidence level, since the p-value is
Clay A1 A2 A3 A4 A5 less than 0.05. Duncan test (Table 5) indicate that calcium hydrox-
Mineralogical composition (%) ide fixation percentage of the excavated clays calcined at 550 °C is
Kaolinite (K) 55 21 53 57 31
Quartz (Q) 40 79 43 39 69
significantly lower than the percentage fixated when they are cal-
FWHM 001 Index 0.23 0.15 0.23 0.27 0.31 cined at 650 °C; because at this temperature it generates more
reactive amorphous phase that produces C-S-H and it gives alu-
minum to the system, to produce other hydrated phases (C2ASH8
60 y C4AH13) that also fix calcium hydroxide [33].
The results of Frattini test are presented in Fig. 8. Excavated
50
550°C 650°C clays (AC1 up to AC5) calcined at 550 °C blended with Portland
cement kind B did not show pozzolanic activity after 2 and 7 days,
Ca(OH)₂ Fixaon (%)

40
because their values for [Ca2+] and [OH–] are located at oversatu-
AC1 rated region above the solubility curve of calcium hydroxide. After
AC2 28 days, the concentration of [CaO] is located at unsaturated region
30
AC3 below the curve, indicating that the calcium hydroxide released by
Portland cement hydration has been consumed and therefore the
20 AC4
calcined excavated clays at that temperature are pozzolanic and
AC5 present activity at later ages.
10
While the calcined excavated clays at 550 °C in the calcium
hydroxide fixation test showed percentages between 20% and
0
28 30% (Fig. 6), the results of the Frattini test show that they do not
7
Hydraon (days) exhibit pozzolanic activity, since this test just consider that there
is activity pozzolanic when the calcium hydroxide fixation per-
Fig. 6. Calcium hydroxide fixation percentage of the calcined excavated clays. centage is more than 30%. The blends of Portland cement kind B
with excavated clays calcined at 650 °C show pozzolanic activity
The statistic evaluation of calcium hydroxide fixation is pre- at early ages because after 7 days the values for [Ca2+] and [OH–]
sented in Table 4, it shows that the calcination temperature effect are located below the solubility curve of calcium hydroxide.
is statistically significant and there are significant differences The procedure used to quantify the Frattini test results is as
between evaluated temperatures at 99.9% confidence level. Fur- described by Donatello et al [34] and Özen et al [35], from the the-
thermore, curing time also affects significantly the calcium hydrox- oretical maximum [CaO] concentration and the [CaO] reduction
ide fixation and there are significant differences between 7 and percentage. The AC1 was the clay more reactive at 7 days when
28 days at 99.9% confidence level. was calcined at 650 °C and at 28 days when it was calcined at

9 9
Combined water (%)
Combined water (%)

8 8
A1 A1
7 7
6 A2 6 A2
5 A3 5 A3
4 A4 4 A4
3 A5 3 A5
2 2
1 1
0 0
0 7 14 21 28 0 7 14 21 28
Curing me (d) Curing me (d)
a) b)
Fig. 7. Combined water for clays calcined at (a) 550 °C and (b) 650 °C.
820 H. Yanguatin et al. / Construction and Building Materials 211 (2019) 814–823

Table 4
Analysis of variance of calcium hydroxide fixation.

Source of variation Parameters Degree of freedom Sum of squares Mean square Value F p-value Significance
% FixCH Sample 4 280.9 70.2 7.6 0,002
Hydration age 1 761.8 761.8 82.4 1.0e 06 Yes
Temperature 1 356.2 356.2 38.5 4.5e 05 Yes
Temper:Hydration 1 50.4 50.4 5.5 0.037 Yes
Residuals 12 110.9 9.25

Table 5 45
Duncan test for calcium hydroxide fixation.
40
Temperature (°C) Mean Groups Curing (days) Mean

Compresive strength (MPa)

650 40.5 a 28 42.5 35
550 32.1 b 7 30.1
30 AC1550
25 AC2550
18 20 AC3550
16 CP 15 AC4550
2d 7d 28d
14 550°C AC1 AC5550
650°C 10
AC2 Control
12 5
[CaO],mm/l

AC3
10 0
AC4 7 days 28 days
8
AC5 Curing me
6 a)
4
45
2
40
Compressive strength (MPa)

0 35
30 50 70 90 110 130
[OH¯], mmol/l 30 AC1650
25 AC2650
Fig. 8. Frattini test on pastes of cement kind B – calcined clay.
20 AC3650
15 AC4650
550 °C, this can be associated with its Blaine specific surface area
(the highest value – 8049 cm2/g) and kaolinite content (one of 10 AC5650
the highest values – 55%). The AC2 and commercial kaolin showed 5 Control
the less reactivity at both temperatures and ages, it related to its
0
lower kaolinite content (21%) and lower specific surface area
7 days 28 days
(5978 cm2/g at 550 °C and 4918 cm2/g at 650 °C). That is, the
results of the Frattini test are in function of both the kaolinite con- Curing me
tent and the specific surface area of the clays. b)
On the other hand, the thermal treatment effect on pozzolanic
Fig. 9. Graphical results of compressive strength of blended mortars a) 550 °C b)
activity measured from the [CaO] reduction percentage was deter- 650 °C.
mined with an experiment design of two factors in randomized
complete blocks (excavated clay kind). The statistic evaluation is
presented in Table 6, it shows that both the calcination tempera-
ture and the test age effect are statistically significant and there at 650 °C is significantly higher than the reduced percentage when
are significant differences between evaluated temperatures at they are calcined at 550 °C, while the reduction percentage at
99.9% confidence level. 28 days is higher than at 7 days.
Interaction between temperatures and curing time is also sta- The graphic results of compressive strength after curing for 7
tistically significant at 99% confidence level. Duncan test indicate and 28 days for mortar of Portland cement kind A blended with
that [CaO] reduction percentage of the calcined excavated clays 20% calcined excavated clays at 550 °C is presented in Fig. 9a and

Table 6
Analysis of variance of Frattini test results.

Source of variation Parameters Degree of freedom Sum of squares Mean square Value F p-Value Significance
% [CaO] Clay 4 310.1 77.5 2.0 0.15
Test age 1 2352.1 2352.1 61.7 4.5e 06 Yes
Temperature 1 804.2 804.2 21.1 0.0006 Yes
Temper:Test age 1 376.9 376.9 9.9 0.0084 Yes
Residuals 12 457.1 38.1
 H. Yanguatin et al. / Construction and Building Materials 211 (2019) 814–823 821

in Fig. 9b it blended with calcined excavated clays at 650 °C, with
error bars indicating ± standard deviation.
All mortars blended with calcined excavated clays at 550 °C and
650 °C have strengths lower than the control mortar at 7 days
because the amount of hydration products does not compensate
the dilution effect; these results are consistent with previous find-
ings by Tironi et al. [31], Alujas et al. [15], Zhou et al. [3], Du and
Pang [20].
The AC4 sample from the clay with the highest kaolinite con-
tent, when was calcined at 650 °C shows statistically the same
strength that mortar control; since the finest particles of metakao-
lin provide actives sites of nucleation and the effect of pozzolanic
reaction is expressed [36]. The AC2 from the clay with the lowest
kaolinite content, developed the lowest strength when was
calcined at both 550 °C and 650 °C.
After 28 days, the AC4 calcined clay at 650 °C has similar
strengths to the control mortar, because at this age it is more
intense the effect due to C-S-H and C-A-S-H phases formation (as
may be noted in Fig. 7b) causing densification and improvement
of the mechanical properties, as proposed by a number of authors
[3,27]. The strengths of each of the five clays calcined at 550 °C are
lower than strengths of the calcined clays at 650 °C (Fig. 10 a-b),
due to at this temperature the fixed percentages of CH are higher
and as a result of both the silica and alumina reactive formation.
The increase percentage of compressive strength (CSI) in the
blended mortars with respect to the control (C) was calculated
according to Uchima et al. [37] and the results for both tempera-
ture and curing time as well as the w/c ratio and are showed in
Table 7, when the calcined clays replace the Portland cement it
generates a rise in the water demand since their greater specific
surface [38,39]. The AC4 clay was tested with a flow lower than
the other ones, because the w/c ratio already was very high affect-
ing its strength.
The increases in compressive strength show that after 7 days
the pozzolanic activity have started for the calcined clays, although
for AC2 and AC4 calcined clays at 550 °C it is not enough to offset
the dilution effect.
Thermal treatment effect on the compressive strength was
determined with an experiment design of two factors in random-
ized complete blocks (excavated clay kind). The statistic evaluation
is presented in Table 8, it shows that both the curing time and the
calcination temperature effect are statistically significant and there
are significant differences between evaluated temperatures at
99.9% confidence level.
Duncan test indicate that compressive strength of the calcined
excavated clays at 650 °C is significantly higher than compressive
strength when they are calcined at 550 °C, while compressive
strength at 28 days is higher than at 7 days.
4. Discussion
The excavated waste clays that were analyzed in this research
contain percentages of kaolinite between 20% and 30% and
between 50% and 60% and they presented mass loss from 2% until
8% when are calcined at 550 °C and 650 °C temperature range. The

45 550 °C 45 550 °C
Compressive strength (MPa)

Compressive strength (MPa)

650 °C AC1 650 °C AC1

40 40 AC2
AC2

35 AC3 35 AC3

AC4 AC4
30 30
AC5 AC5

25 25
20 25 30 35 40 30 35 40 45 50 55
Ca(OH)2 Fixaon (%) Ca(OH)2 Fixaon (%)

a) b)
Fig. 10. Relationship between compressive strength and CH fixation a) 7 days b) 28 days.

Table 7
Increase percentage of compressive strength of blended mortars.

Age (days) C 550 °C 650 °C

AC1 AC2 AC3 AC4 AC5 AC1 AC2 AC3 AC4 AC5
7 – 8.3 7.2 8.1 3.7 18.6 9.6 11.7 15.9 20.7 7.3
28 – 12.9 3.0 10.7 7.1 15.7 15.7 11.3 16.4 24.0 14.0
w/c 0.48 0.53 0.51 0.51 0.55 0.51 0.51 0.5 0.51 0.5 0.52
Flow (%) 107 112 115 108 95 107 105 115 108 104 111

Table 8
Analysis of variance of compressive strength results.

Source of variation Parameters Degree of freedom Sum of squares Mean square Value F p-Value Significance
CS Clay 4 18.7 4.7 1.3 0,32
Curing time 1 209.4 209.4 58.6 5.9e 06 Yes
Temperature 1 23.5 23.5 6.6 0.02 Yes
Temper:Curing 1 0.05 0.05 0.01 0.90
Residuals 12 42.9 3.6
822 H. Yanguatin et al. / Construction and Building Materials 211 (2019) 814–823
calcination at 550 °C of excavated clays increases the specific sur-
face Blaine on average 16.6% relative to the raw clays, phenomenon
that can be explained because the dehydroxylated particles tend to
aggregate and create new porous grain with a high specific surface,
supporting previous findings in the literature [6,40–41].
There exists a certain direct relationship, but it is not definitive,
between the calcium hydroxide fixation percentages and the
kaolinite content; calcined clays from excavated clays with kaolin-
ite contents between 20% and 30% after 28 days fixed percentages
between 32% and 42%, while those from kaolinite contents
between 50% and 60% fixed percentages between 40% and 50%.
Similarly, also there seems to be a relationship between the cal-
cium hydroxide fixation percentages and the specific surface area
Blaine; the clay calcined at 650 °C with the lowest specific surface
(4918 cm2/g) fixed 38% after 28 days, while the calcined clays with
specific surfaces higher than 5100 cm2/g fixed percentages
between 46% and 50%.
The increase percentage of compressive strength from 8% until
19% at 7 days in the mortars of Portland cement kind A blended with
excavated clays calcined at 550 °C, corresponds the filler effect since
these clays did not show pozzolanic activity in the Frattini test. After
28 days, all mortars blended with calcined excavated clays increase
the compressive strength until 25%, due to the formation of C-S-H
and C-A-S-H phases, determined by the combined water.
The excavated clays with high kaolinite contents (A1, A3 and
A4) show different pozzolanic activity because in addition to min-
eralogical composition, other characteristics such as the degree of
structural disorder and specific surface Blaine are important. The
FWHM index of A4 clays (0.27) is the highest in this group so it
presents less structural order and this contributes to increase its
pozzolanic activity.
The differences among the compressive strength, calcium
hydroxide fixation and the Frattini test are based on sensitivity of
this later for to determine the contribution of the pozzolanic reac-
tion, that it is influenced by both the chemical composition of exca-
vated clay and the Portland cement alumina content [33,42].
5. Conclusions
Excavated waste clays with kaolinite content between 20% and
30% can be used as supplementary cementitious materials when
they are calcined at 550 °C for 1 h and also when they are calcined
at 650 °C for 3 h, obtaining at 7 days percentages of calcium
hydroxide fixation on average 23% and 33%, respectively.
The calcium hydroxide fixation percentage at 7 of the excavated
clays calcined at 650 °C is on average 8% higher than the percent-
age fixed by the calcined clays at 550 °C, according to the Duncan
test, stating that pozzolanic reactivity improved as calcination
temperature increased.
The Frattini test determines the pozzolanic activity of calcined
excavated clays when the calcium hydroxide fixation percentage
is higher than 30%, while the contribution of pozzolanic reaction
can be seen in the increase percentage of compressive strength.
The replacement of Portland cement in mortars with calcined
excavated clays generates increases percentage of compressive
strength due to the both filler effect and the chemical effect that
appears as a result of the pozzolanic reaction between metakaolin
and the calcium hydroxide to form hydrated phases. The increase
percentage of compressive strength at 7 days for the calcined exca-
vated clays at 550 °C is on average 9%, meanwhile when they are
calcined at 650 °C, the increase percentage is on average 13%.
Conflict of interest
None.
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