Jadcr.18.00246 Thermal Analysis

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10.1680/jadcr.18.00246
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10.1680/jadcr.18.00246
Submitted: 22 December 2018
Published online in ‘accepted manuscript’ format: 19 August 2019
Manuscript title: Thermal Activation Mechanism and Pozzolanic Activity Characteristics of
Coal Flotation Tailing
Authors: Dongxue Liu1,2, Yang Huang1,3, Junyang Hu4, Qiming Feng1,2 and Junhui Xiao1,3
Affiliations: 1School of environment and resources, Southwest University of Science and
Technology Sichuan Mianyang, China; 2Key Laboratory of Solid Waste Treatment and
Recycling, Ministry of Education, Sichuan Mianyang, China; 3Sichuan Engineering Lab of
Non-metallic Mineral Powder Modification and High-value Utilization, China and

4
Environmental Protection Bureau, Sichuan Guangyuan Cangxi, China
Corresponding author: Yang Huang, School of environment and resources, Southwest
University of Science and Technology Sichuan Mianyang 621010, China. Tel.:
+86-139-9011-2461.
E-mail: swusthy@163.com
10.1680/jadcr.18.00246
Abstract
The Coal flotation tailings (CFT) were calcined to utilize it as supplementary cementing materials. CFT and its
calcined products were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD) and
Fourier transforms infrared spectroscopy (FTIR). The pozzolanic activity of calcined products was analyzed by
the strength activity index (SAI). The hydration products of blended cement were characterized by TGA, XRD
and SEM to explain the influence calcined products on cement hydration. The results showed that calcination
treatment destroyed the structure of illite-kaolinite mixed-layer clays from CFT and enhance pozzolanic activity.
Moreover, the highest pozzolanic reactivity was obtained at 850°C because recrystallization effect increased
chemical stability above 900°C. The impact of calcined CFT on the hydration of cement in a blended system
was the combination of micro-aggregate effects and the pozzolanic reaction. The experimental results indicated
that calcined products of CFT had good pozzolanic activity, which provided the feasibility of large-scale
recycling utilization of CFT.
Keywords: Calcined clays; Portland cement; Pozzolans; Thermal analysis
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1. Introduction
Cement is often regarded as the primary material of the construction industry, making the
production of cement one of the most energy-intensive industrial sectors and also one of the
largest contributors to CO2 emissions and air pollution. The cement industry requires
expending tremendous energy, releasing extreme amounts of environmental pollution, which
makes it one of the most environmentally unfriendly industries that currently exists. Although
cement itself has a lower negative environmental impact compared to other alternative
construction materials, the sheer volumes of cement and concrete produced because cement
production to account for some 5%-8% of non-natural CO2 emissions (Karen LS et al., 2008).
Many researchers have searched for new cement materials that possess greater strength and
durability by using innovative chemical admixtures and supplementary cementing materials
(SCMs). One of the main areas of interest for sourcing new raw materials has been found by
using by-products from other industrial sectors, resulting in a search that promotes large-scale
rotation of industrial waste in productive cycles that has become a central economic initiative
(Liu S et al., 2014). Industrial by-products such as fly ash and blast furnace slag have been
widely used as auxiliary cementitious materials (Grzegorz G, 2017; Torres-Gómez Ana et
al.,2016; Lafond E et al.,2017; Bong S C et al.,2017; Schneider NS et al.,2016), but the
reserves or production of these materials cannot meet the growth of cement demand. Their use
as SCM in concrete is limited by regional availability and high cost, and their availability is
dependent on the degree of economic development in the region in which they are produced
(Schneider M et al., 2008).
A variety of research has defined pozzolans as silica-aluminous materials which react
chemically with calcium hydroxide at ambient temperature to form compounds with
cementitious properties, which can be incorporated into concrete as an additive or as a partial
cement replacement (Záleská M et al., 2018; Hailong W et al., 2016).However, natural
pozzolan is conditioned by local geology and is available only in certain regions
(Rodrguezcamacho R E and Uribeafif R, 2002).Within this context, calcined clays as
supplementary cementing materials (SCMs) were studied due to their relatively good
geographical distribution and their proven pozzolanic properties under specific calcination
conditions (Vejmelková E et al., 2004; Tironi A et al., 2013; Hollanders S et al., 2016).After
thermal activation of clay minerals, they will achieve some disordered alumina and silica-rich
phases, which show pozzolanic activity (Paulo Sérgio Lima Souza and Molin D. C. C. D,
2005). Highly-reactive pozzolans have the potential to usher in a transformation of the
concrete industry. Most of the research on calcined clays focused on the relationship between
specific clay minerals (mainly kaolinite, montmorillonite, and illite), calcination temperatures,
and pozzolanic reactivity. Those studies have shown that kaolinite has the highest pozzolanic
activity and a lower activation temperature (Souri A et al., 2015; Liu Y et al., 2017), followed
by montmorillonite (Fernandez R et al., 2011), while illite (He C et al., 1994) and
mixed-layer mica/smectite (He C et al., 2000) exhibit pozzolanic reactivity even at high
calcination temperatures. Utilization of these materials in cement/concrete not only leads to a
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reduction in carbon dioxide emissions, but also lowers costs and enhances the properties of
concrete in the fresh and hardened states.
In Sichuan province in China, several million tons of coal flotation tailings (CFT) every
year were separated from the coal ore and disposed in tailings ponds, which occupied an
enormous amount of land and caused pollution of surface and underground water. Although
the water content of CFT is as high as 20-30%, but the calorific value is in the range of
1500-2500 kcal/kg and it is fine particle size distribution, which is very beneficial for further
utilization. Especially, the CFT contain 60% clay minerals, such as illite and kaolinite,
implied that it is suitable for the preparation of SCMs. However, at present, there are neither
detail research reports nor industrialized application on this kind of CFT as SCMs by calcined
treatment. The objective of this research is to understand the thermal activation mechanism of
CFT by calcination treatment, evaluate the pozzolanic activity of calcined products and
characterize the hydration characteristics of blended cement. The results will provide
important basic conclusions for industrial utilization of CFT.
2. Experimental section
2.1 Raw Materials

The CFT from coal preparation process were collected from the Sichuan Coal
Guang-Wang Group in northern Sichuan, China. The CFT studied was dark grey with
extremely fine grain size (shown in Table 1), which was saving energy consumption for
crushing utilization. Several of his physical and chemical properties of CFT were as follows:
20% moisture content, 31.3% loss of ignition, 1875 kcal/kg calorific value and 19 plasticity
indexes, which provided favorable conditions for granulation and calcination. The results of
X-ray diffraction (XRD) of CFT are showed in in Figure 1, indicated that the presence of
illite, kaolinite, quartz, and calcite. The chemical and mineralogical composition of materials
of CFT analysis is summarized in Table 2. The content of coal is 12 wt. %. The results showed
that the main chemical compositions of raw materials are SiO2 and Al2O3, accounted for
55.5%. The content of kaolinite, illite, quartz and calcite were about 30, 25, 23 and 8 wt. %,
respectively. The reference cement used in this experiment is an ordinary Portland cement
(OPC) produced by China United Cement Qufu Co. Ltd. ISO standard sand is purchased from
Xiamen ISO standard sand Co., Ltd.
2.2 Experiment Methods

CFT was made into rod-like granules (diameter: 3mm) by extruding and granulating and
then dried at 105 °C for 24 h for future use. CFT was calcined at variable temperature ranging
between 700 and 950 °C by SGM2854H box resistor-stove. During the calcination, the
samples were aerated intermittently to decompose the carbon completely. Once the
temperature reaches the specified calcination temperature, it was aerated every 20 minutes.
When the temperature in the furnace reached the set temperature, the CFT were taken out after
a certain period of heat preservation and then placed in ambient air for natural cooling. Then,
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the calcined CFT was ground to a specified particle size by a BJ-400A high speed pulverized
mill. Then it was measured particle size distribution by a U.S.A LS13 320 laser particle sizer.
The pozzolanic activity was determined by the strength activity index (SAI) index of
28d cement mortar. Preparation method of cement mortar is presented as follows:
compressive strength was assessed on mortar cubes (40 × 40 × 160 mm) made with standard
sand (1:3) and a water/cementing material ratio of 0.50. Cement mortar were prepared using
OPC. The blended cement was composed by 30% of calcined products and 70% of Portland
cement. The mortar was mixed in a planetary orbital mixer for 5 min and the specimens
molded and compacted according to Chinese National Standard GB/T 1596 – 2005. The
mortars were first cured in a fog room at 20°C and 95% relative humidity for 24 h, and then
they were stripped from their molds and placed in water at 20 °C until testing ages. At the age
of 3, 7 and 28 days, the compressive strengths were measured the average of three specimens
using universal testing machine ETM-305F-Z. Finally, the strength activity index (SAI) was
calculated as the ratio of the compressive strength of blended cement mortar (A) to the
strength of the OPC mortar (B) at the same age, as percentage. Hydration mechanisms of the
cement pastes with different samples were studied by TGA, XRD and SEM. Preparation
process of cement paste is presented as follows: The hydration products of samples were
prepared on pastes cubes (20 × 20 × 20 mm) made with a water/cementing material ratio of
0.5. The cementing material consisted in a blend of 30% by mass of calcined products under
different calcined conditions pastes and 70% of OPC. When the specified curing ages were
reached, the samples were then immersed in ethanol to stop hydration of the samples. SEM,
XRD, and TGA of cement pastes were tested, and it was observed whether the calcined
products had an impact on cement hydration.
The chemical compositions of CFT were determined by the Axios wavelength dispersive
X-ray fluorescence spectrometer of PANalytical B.V. The phase composition of sample was
analyzed by Panalytical X’pert Pro diffractometer using Cu-Kα graphite-monochromatized
radiation (λ = 1.5418 Å) in the 2θ range 3– 80° (step size: 0.02° 2θ, time per step: 0.8 s).
Thermal behaviors of samples were examined using American STA 449F5 thermal analyzer.
The samples were heated at a constant rate of 10°C/min with an argon flow rate of 50 mL/min
from ambient temperature to 1000°C in air atmosphere. Data obtained by TGA was used to
determine the optimum range of calcination temperatures of each sample and the weight loss of
each sample. The FTIR of CFT was collected by Perkin Elmer Spectrum 400 on the solid
sample using a KBr pressed disk technique over the wave number range of 4000 cm−1 to 400
cm−1. Microscopic morphology of hydration products was observed by the Leica Cambridge
LTD Sigma300 SEM.
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3. Results and discussion
3.1Thermal Activation Mechanism

The thermogravimetric analyses (TGA) of CFT are presented in Figure 2. In the TG
curve, the mass loss is 4.5 wt. % at below 100°C, corresponded with the removal of water
adsorbed from CFT surface. While, in the DTG curve, endothermic peak is weak during this
desorption process. The second significant the mass loss in the TG curve is 7.79 wt. % in the
temperature range 100-400°C, which is associated with the volatile component and
decarboxylation of coal. The third significant the mass loss in the TG curve was 4.5% in the
temperature range 400-600°C, which is associated with de-hydroxylation of kaolinite and
decomposition of coal. The center of the endothermic peak was located at 510°C in the DTG
curve. The fourth event in the TG curve is located in the temperature range 600-900°C, the
mass loss was 4.5 wt. % due to decomposition of calcite, dehydroxylation of illite and
formation of metakaolin (He C et al., 1994). The center is located at approximately 704°C in
the DTG curve. The last effect is recorded in the DTG curve a small shoulder peak appeared
at 923°C, which may relate to recrystallization melilite formation. The center of the
endothermic peak is located at ca. 923°C in the DTG curve. An extended high temperature
endothermic reaction from below 900°C to over 1000°C, without an obvious weight loss,
may be due to destruction of illite structure. The position of the dehydroxylation peak mainly
depends on the type and combination of the hydroxyl groups present in the sample, whereas
the shape and range of the dehydroxylation peak mainly depends on the crystallinity or
particle size distribution (Du H J and Pang S D, 2018). According to the results of
thermogravimetric analyses, we carry out calcination experiments from 700 and 950 °C.
Figure. 3 presents the XRD patterns of CFT after calcination in the 700-950°C range, as
well as the XRD patterns of the CFT (shown in Figure 3). And from these results it is found
that the characteristic diffraction peak of kaolinite disappears at 700°C, indicate that the
kaolinite transformed into metakaolinite. Previous studies have shown that metakaolinite
crystals have the same shape as kaolinite, but the difference is that its structure is highly
defective after dehydroxylation and this causes vanishing of the XRD reflections. The
characteristic diffraction peak of illite gradually weakens above 700°C, and or even
disappears at 950°C, suggesting that the structural damage to illite inflicted by
dehydroxylation (He C et al., 1994). This result is consistent with that reported in the
literature, which proves that the activation temperature of illite is higher than kaolinite (He C
et al., 1994; Yang H et al., 2010). The calcite peak decreases with increasing temperature and
disappears completely at 900°C. The melilite is observed from the XRD patterns of calcined
products at 900°C and 950°C, which imply the recrystallization of the calcined products and
might reduce pozzolanic activity. Further, after carefully compared with 900°C, the melilite
reflection becomes more remarkable at 950°C, which correspond to the diminished of
reflections of illite. Due to destruction of crystalline phases by calcination results in the
formation of amorphous substances, it can be inferred that the degree of disorder of the
calcined products was highest at 850°C which may have high pozzolanic.
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Figure 4 present the FTIR spectroscopy of CFT after calcination in the 700-950°C
range, as well as the FTIR spectroscopy of the CFT. The spectra for the sample exhibited the
following characteristic bands: O-H stretching vibrations at 3697 cm-1, 3621 cm-1 and 3436
cm-1; C-O stretching vibrations at 1633 cm-1; Si-O-Si stretching and bending vibrations at
1084 cm-1 ,798 cm-1 and 778 cm-1; Si-O vibrations at 1031 cm-1 ,1002 cm-1,695 cm-1and 470
cm-1; Al-OH bending vibrations at 913 cm-1; Si-O-Al bending vibrations at 535 cm-1 (Souri A
et al., 2015; Yang H et al., 2010). According to the study of Huaming Yang, the band at 3695
cm−1 was related to the stretching vibration of hydroxyl groups at the edges of the kaolinite
platelets and the O-H band at 3621 cm-1 was related to the stretching vibration of hydroxyl
groups at the edge of kaolinite (Marel V D H W and Beutelspacher H ,1976). According to
the study of Huaming Yang, it believed that the band at 3436 cm-1 was attributed to lattice
defects either due to isomorphous substitution of foreign cations or imperfections of the illite
lattice structure (Yang H M et al., 2010). However, the 3436 cm-1 band was tiny and is not
observed in many FTIR spectra of different types of layered clays. Marel H. W. considered
that this spectral band might be due to loosely absorbed water molecules (Zhang J X et al.,
2009). None of the O-H bands are present on the spectra of the products calcined at
temperatures above 700°C, which indicates that CFT were dehydroxylation. In the samples
with calcination temperatures exceeding 700°C, some hairlike displacements in lattice
vibrations around 1000 cm-1 attributed to Si-O vibrations are also observed, indicating that
self-adjustment or rearrangement on the CFT lattice may have occurred. A broader band
appearing at 1100 cm−1 is due to the dimerization of silica tetrahedrons induced by thermal
treatment (Cao Z et al., 2016). Samples calcined over 900 °C lack the band at 913 cm−1,
which indicate the breakages of Al-OH bands in the thermally-treated CFT. Samples calcined
at 950°C lack a band at 535 cm-1, which indicates that the Si-O-Al bolds have been broken in
the thermally-treated CFT. Therefore, the characteristic peaks of kaolinite and illite
disappeared, and the CFT structure is destroyed when the calcination temperature is 950°C,
which is consistent with the XRD results.
3.2 Pozzolanic activity and hydration mechanism
3.2.1 Mechanical strength test of cement mortar.

In order to understand the effect of treatment process on pozzolanic activity of the CFT
products, calcination temperature, calcination time and grinding time are studied. The
relationships between calcination temperature and 28d cement `mortar activity index is
shown in Table 3, when the calcination temperatures were different temperature, the
calcination time was two hours, and the grinding time was 30min. According to Table 3,
along with temperature rise, the 28d flexural strength and compressive strength of cement
mortar first increases and then decreases. When the calcination temperature is 850°C, the 28d
activity index of the samples reaches 94.54%. Combined with the results of XRD, it is found
that the CFT sample calcined at 700-850°C contributes to promote the 28d activity index, and
the activity starts to decrease with the formation of melilite when the heating temperature is
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over 850°C. Generally, the cementitious activity benefits from the decrease of the degree of
sinter. When the calcination temperature exceeds 900°C, the full crystal structure of samples
is strengthened by chemical stability, although the degree of Si-O polymerization of clay
minerals with a chip structure is not high (Zhang J X et al., 2009).
Calcined products kept for different heat preservation times at 850°C were ground to 30
min and the pozzolanic activity was measured. The relationships between calcination times
and 28d cement mortar activity index is shown in Table 4. According to Table 4, when
extending calcination time, the activity indices of samples first rise and then decline. When
the calcination time is 1.5 h, the mortar strength is the highest, close to the control cement
mortar strength, and the activity index is 98.52%. The activity is relatively low when the
calcination time is less, which can due to incomplete decomposition of kaolinite and
unburned carbon (Cao Z et al., 2016). Ch. Bich et al. pointed out that the dehydroxylation
degree of kaolin is incomplete with insufficient calcination time and hence makes calcined
products inert (Cao Z et al., 2009).
The relationship between grinding time and 28d cement mortar activity index is shown
in Table 5, when the calcination temperature is 850°C, the calcination time is 1.5 hours. From
Table 5, it is shown that the longer the grinding time, the smaller the particle size, the higher
the 28d activity index. The stronger the mechanical activation, the greater the enhancing
effect on the activity of the product ash. It has been shown previously that the pozzolanic
activity of samples can be improved by extending the grinding time (Yongdan C et al.,
2017).The work of Ferreiro S, et al showed that fineness of the calcination clay had a
noticeable effect on the long-term reaction degree of the resulting calcined particles, which
was evident in data on strength development of the blended cements in mortar (Adamiec P et
al., 2008). It is shown that the finer the particles of the calcined clay, the higher the strength
index. Despite increasing the fineness of the sample was beneficial to improving its
pozzolanic activity, when the grinding time is longer than 30 minutes, the 28-day activity
index tends to be stable and the change is not obvious. In the actual production process, the
optimum fineness should be determined by taking into account the pozzolanic effect,
production cost, and water requirement of cement. In order to cost-saving, the grinding time
is better to be 30 minutes.
Therefore, the optimal condition are the calcination temperatures was 850°C, the calcination
time was two hours, and the grinding time was 30min.
3.3.2 TGA.
It is generally believed that the mechanism of cement strength enhancement by SCMs is
through pozzolanic reaction and micro-aggregate effect. Among the two effect, the
pozzolanic reaction is Ca(OH)2 generated during cement hydration with pozzolanic material
to form a C-S-H gel (Fan Y et al., 1999), which has been well-reported in research concerning
fly ash cement and slag cement hydration (Chindaprasirt P et al., 2004; Fraire-Luna P E et al.,
2006). Further, previous studies show that the higher the content of Ca(OH)2 in hardened
cement, its strength is more lower during pozzolanic reaction. Therefore, in accordance with
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this principle, the contents of Ca(OH)2 and C-S-H gel in hardened cement paste can indirectly
predict the pozzolanic activity of calcined CFT products. Based on this, hydration products of
blended cement with calcined CFT at different calcination condition are characterized by
TGA to evaluate the contents of Ca(OH)2 and C-S-H gel in hardened cement paste.
The DTG and TG curves of 28d cement paste samples made of calcined CFT under
different temperature are showed in Figure 5. As shown in Figure 5, three endothermic
reaction phases are observed in 100-400°C, 400-500°C, and 650-750°C, respectively. The
first temperature range in the 100-400°C corresponds to the temperature for bound water
desorption of C-S-H and a small amount of ettringite (AFt) and a small shoulder peak around
120°C is generated when unbound water desorbs from samples (Singh M and Garg M, 1995;
Heikal M, 2006). The second temperature range in the 400-500°C appears as a result of the
decomposition of Ca(OH)2.The third temperature range in the 650-750°C is caused
decompose peak of CaCO3. According to weight loss values within the three temperature
ranges in Table 6, it can be inferred that the sample calcined at 850°C are the highest
pozzolanic activity. The reason is that the consumption of Ca(OH)2 and generation of C-S-H
depend on pozzolanic activity of calcined products. The estimated content of Ca(OH)2 and
C-S-H gel in hardened cement was about 1.81 and 7.09 wt.%., respectively. In addition, as
shown in Figure 5b, along with the rise of the calcination temperature, from weight loss rate
(DTG) curve it can be seen that the weight loss rate of Ca(OH)2 is the smallest and that of
C-S-H is the largest at 850 C. This is also consistent with the activity index of 28d cement
mortar in Table 3.
The TGA of 28d cement paste made from calcined CFT blended with different calcination
times are showed in Figure 6. It can be found that the TGA is same with the calcined
products under different temperature, which three endothermic reaction phases is in
100-400°C, 400-500°C, and 650-750°C, respectively. For further understanding weight loss
behaviors of hydration products, the weight loss values within the three temperature ranges is
listed in Table 7 According to Table 7, The sample calcined for 1.5 h is the largest weight
loss in the 100-400°C temperature range, which The estimated content of C-S-H gel in
hardened cement was about 7.84wt.%. The sample calcined for 1.5 h display the least weight
loss in the 400-500°C temperature range, which the estimated content of Ca(OH)2 in
hardened cement was about 1.79 wt.%.The results indicate that the pozzolanic activity of
sample calcined for 1.5 h is the highest due to the consumption of Ca(OH)2 and generation of
C-S-H. As shown in Figure 6b, along with extending calcination time, from weight loss rate
(DTG) curve it can be seen that the weight loss rate of Ca(OH)2 is the smallest and that of
C-S-H is the largest for 1.5 h. This is consistent with the activity index of 28d cement mortar
in Table 4.
The TGA of 28d cement paste made from calcined CFT blended with different grinding time
are showed in Figure 7. In order to understand the weightlessness behavior of hydration
products, the weight loss values within the three temperature ranges is listed in Table 8.
According to Table 8 shown that the longer the grinding time, the larger the weight loss in the
100-400°C temperature range, while the smaller the weight loss in the 400-500°C
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temperature range. The results indicate that the smaller the particle size, the greater the effect
on the consumption of Ca(OH)2 and generation of C-S-H. When the grinding time is 120
minutes, the estimated content of Ca(OH)2 and C-S-H gel in hardened cement was about 1.25
and 9.36 wt.%., respectively. As shown in Figure 7b, along with extending grinding time,
from weight loss rate (DTG) curve it can be seen that the weight loss rate of Ca(OH)2 is
getting smaller and smaller, and that of C-S-H becomes larger and larger. Despite increasing
the fineness of the sample was beneficial, when the grinding time is longer than 30 minutes,
the content of Ca(OH)2 and C-S-H to be stable and the change is not obvious. This is
consistent with the activity index of 28d cement mortar in Table 5. Since the effect of
increasing energy consumption and cost of grinding on the 28d activity index is not
significant, the fineness of grinding is recommended to reach D90=20μm.
3.3.3 XRD.
On the base of the above studies of research, we determined the optimum calcination
conditions. In order to compare the difference of hydration products produced by pure cement
paste and calcined products under optimal condition blended cement paste, their hydration
products were further studied by XRD and SEM. Figure 8 displays the hydration products of
different hydrated cement paste for different ages by XRD. The main hydration products are
basically the same in each sample and include ettringite (AFt), portlandite (Ca(OH)2),
calcium silicate hydrate (C-S-H) and unreacted admixtures. As shown in Figure 8, the pure
cement paste and calcined products blended cement paste along with extending ages, the peak
intensity of calcium hydroxide is lower and lower, and the peak intensity of ettringite and
hydrated calcium silicate is higher and higher. These results can be combined with Figure 9
to analyze the hydration degree of cement paste samples under different ages, and it is found
that the illite is not observed in the XRD spectra. It may not be due to the hydration reaction
between illite and calcium hydroxide. Which has been shown to be low in hydration activity
according to the literature (He C et al., 1994; Yang H et al., 2010), but is likely because the
diffraction peaks are covered or merged.
3.3.4 SEM.
The SEM images of pure cement paste and the best calcined products blended cement
paste at 3,7and 28 days were shown in Figure 9 .Ca(OH)2 crystals are hexagonal sheets and
an image layer can be seen in Figure 9,which shows that the amount of Ca(OH)2 decreases
with increasing cure time because Ca(OH)2 converts to dense C-S-H (Manjit Singh and
Mridui Garg, 1995; Papadakis V G et al., 1999). The ettringite crystal shows a characteristic
needle shape, and the amount of such needles decreased with the curing time
(Escalante-Garcı ´a et al., 2010). The results show that the microstructure of cement pastes
had become denser and stronger at 28 days, and the addition of products calcined at 850°C
promoted the formation of C-S-H in the stages of cement hydration. This product then
cemented with other hydrated products such as ettringite and calcium hydroxide, which
accelerates the formation of the cement paste structure, promote slurry condensation, and
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reduce slurry fluidity, thereby playing a strength role. Although it is difficult to observe
calcined illite using an SEM, when combine with phase analysis of hydration products, it is
inferred that illite mainly displays a micro-aggregate effect in the hydration products (Marel
V D H W and Beutelspacher H ,1976). Comprehensive mechanical tests and hydration
mechanism analysis supports that mechanical and thermal activation treatments can improve
the hydration reactivity of the CFT and the strength of the mixed cement can be enhanced by
pozzolanic activity and physical filling.
4. Conclusions
The investigation on coal flotation tailings from in northern Sichuan used for the
preparation of pozzolanic material by mechanical activation and thermal activation, showed
that the inert material (CFT) can be made to display pozzolanic activity by altering the
grinding time, calcination temperature, and holding time. The de-hydroxylation behavior of
CFT occurred at 700°C, and the pozzolanic activity of CFT is further increased at 850°C. The
results of the cement strength activity index test and the content of hydration products
analysis, which show that the optimal calcinations condition are the calcination temperatures
was 850°C, the calcination time was two hours, and the grinding time was 30min. TGA,
XRD and SEM analysis of the hydration of blended systems could conclude that the calcined
products had pozzolanic activity and could consumed calcium hydroxide by pozzolanic
reaction. It is shown that the smaller the particle size, the higher the pozzolanic activity index,
the more consumed calcium hydroxide. Moreover, incorporating calcined CFT into a cement
admixture cannot only consume large quantities of CFT, but can potentially also save many
natural resources for the cement clinker. To a great extent, this can solve the urgent problems
that coal mining and enterprises in many places in northern Sichuan need to deal with to
realize the reuse of CFT waste has important economic and environmental significance.
Acknowledgments
This study was financially supported by Foundation Project for Full-time Scientific
Research Innovation Team Construction of Key Laboratory of Ministry of Education for
Solid Waste Treatment and Resource Recovery (14tdgk04).
10.1680/jadcr.18.00246
References
Adamiec P, Benezet J. C and Benhassaine A (2008) Pozzolanic reactivity of silico-aluminous
fly ash. Particuology 6(2): 93-98.
Bich C, Ambroise J and Péra J (2009), Influence of degree of dehydroxylation on the
pozzolanic activity of metakaolin. Applied Clay Science 44(3-4):0-200.
Bong S C, Hoon H L and Young C (2017) Effects of aluminate rich slag on compressive
strength, drying shrinkage and microstructure of blast furnace slag cement. Construction
& Building Materials 140:293-300.
Cao Z, Cao Y, Dong H et al. (2016) Effect of calcination condition on the microstructure and
pozzolanic activity of calcined coal gangue. International Journal of Mineral Processing
146:23-28.
Chindaprasirt P, Homwuttiwong S and Sirivivatnanon V (2004) Influence of fly ash fineness
on strength, drying shrinkage and sulfate resistance of blended cement mortar. Cement &
Concrete Research 34(7): 1087-1092.
Du H J and Pang S D (2018) Value-added utilization of marine clay as cement replacement
for sustainable concrete production. Journal of Cleaner Production 198: 867-873.
Escalante-Garcı ´a, A. Fuentes, A. Gorokhovsky et al. (2010) Hydration Products and
Reactivity of Blast‐Furnace Slag Activated by Various Alkalis. Journal of the
American Ceramic Society.2010 (86):2148-2153.
10.1680/jadcr.18.00246
Fan Y, Yin S, Wen Z et al. (1999) Activation of fly ash and its effects on cement properties11
this article is being published without the benefit of the authors’ review of the proofs,
which was not available at press time. Cement & Concrete Research 29(4): 467-472.
Fernandez R, Martirena F and Scrivener K L (2011) The origin of the pozzolanic activity of
calcined clay minerals: a comparison between kaolinite, illite and montmorillonite.
Cement and Concrete Research 41(1): 113-122.
Fraire-Luna P E, Escalante-Garcia J I and Gorokhovsky A (2006) Composite systems
fluorgypsum–blastfurnance slag–metakaolin, strength and microstructures. Cement and
Concrete Research 36(6): 1048-1055.
Grzegorz G (2017) Generalized fracture toughness and compressive strength of sustainable
concrete including low calcium fly ash. Materials 10(12): 1393.
Hailong W, Xiaoyan S,Junjie W et al.( 2016) Permeability of Concrete with Recycled
Concrete Aggregate and Pozzolanic Materials under Stress. Materials 9: 252.
He C, Makovicky E and Osbæck Bjarne (2000) Thermal stability and pozzolanic activity of
raw and calcined mixed-layer mica/smectite. Applied Clay Science 17(3): 141-161.
He C, Makovicky E and Osbæeck B (1994). Thermal stability and pozzolanic activity of
calcined illite. Applied Clay Science 9(3):0-187.
Heikal M (2000) Effect of temperature on the physico-mechanical and mineralogical
properties of homra pozzolanic cement pastes. Cement & Concrete Research 30(11):
1835-1839.
10.1680/jadcr.18.00246
Hollanders S, Adriaens R, Skibsted J et al. (2016) Pozzolanic reactivity of pure calcined
clays. Applied Clay Science 132:552-560.
Karen LS and R James K (2008) Innovation in use and research on cementitious material.
Cement & Concrete Research 38:128-136.
Lafond E, Coumes C C, D Gauffinet S et al. (2017).Solidification of ion exchange resins
saturated with Na +, ions: comparison of matrices based on portland and blast furnace
slag cement. Journal of Nuclear Materials 483(2017):121-131.
Liu S, Kong Y and Wang L (2014) Hydration mechanism of low quality fly ash in
cement-based materials. Journal of Central South University 21(11): 4360-4367.
Liu Y, Lei S, Lin M et al. (2017) Assessment of pozzolanic activity of calcined coal-series
kaolin. Applied Clay Science 143:159-167.
Manjit Singh and Mridui Garg (1995) Activation of gypsum anhydrite-slag mixtures. Cement
& Concrete Research 25:332-338.
Marel V D H W and Beutelspacher H (1976) Atlas of infrared spectroscopy of clay minerals
and their admixtures. Engineering Geology 11(2): 156-157.
Papadakis V G, Pedersen E J and Lindgreen H (1999) An AFM-SEM investigation of the
effect of silica fume and fly ash on cement paste microstructure. Journal of Materials
Science 34:683-690.
10.1680/jadcr.18.00246
Paulo Sérgio Lima Souza and Molin D. C. C. D (2005). Viability of using calcined clays,
from industrial by-products, as pozzolans of high reactivity. Cement and Concrete
Research 35(10): 1993-1998.
Rodrguezcamacho R E and Uribeafif R (2002) Importance of using the natural pozzolans on
concrete durability. Cement & Concrete Research 32(12): 1851-1858.
Schneider M, Romer M, Tschudin M et al. (2011) Sustainable cement production—present
and future. Cement & Concrete Research 41(7): 642-650.
Schneider NS and Dietmar S (2016) Studying the Hydration of a Retarded Suspension of
Ground Granulated Blast-Furnace Slag after Reactivation. Materials 9: 933.
Singh M and Garg M (1995) Activation of gypsum anhydrite-slag mixtures. Cement &
Concrete Research 25(2):332-338.
Souri A, Golestani-Fard F, Naghizadeh R et al. (2015) An investigation on pozzolanic
activity of Iranian Kaolins obtained by thermal treatment. Applied Clay Science 103:
34-39.
Tironi A, Trezza M A, Scian A N et al. (2013). Assessment of pozzolanic activity of different
calcined clays. Cement & Concrete Composites 37(1): 319-327.
Torres-Gómez Ana, Enrique L,Rocio O et al. (2016) Combined effects of non-conforming fly
ash and recycled masonry aggregates on mortar properties. Materials 9(9): 729.
Vejmelková E, Keppert M, Rovnaníková P et al. (2004). Application of burnt clay shale as
pozzolan addition to lime mortar. Cement & Concrete Composites 26:486-492.
10.1680/jadcr.18.00246
Yang H M, Yang W G, Hu Y H et al. (2010) Effect of Mechano chemical processing on Illite
Particles. Particle & Particle Systems Characterization 22: 207-211.
Yang H, Yang W., Hu Y et al. (2010). Effect of mechanochemical processing on illite
particles. Particle & Particle Systems Characterization 22(3): 207-211.
Yongdan C, Yanxin L I, Jinshan Z et al. (2017) Effects of Calcination Temperature and
Particle Size on Pozzolanic Activity and Microstructure of Coal Gangue. Journal of the
Chinese Ceramic Society 8(45):1153-1158.
Záleská M, Pavlíková M, Pavlík Z et al. (2018) Physical and chemical characterization of
technogenic pozzolans for the application in blended cements. Construction & Building
Materials 160:106-116.
Zhang J X, Sun H H, SunY M et al. (2009) Correlation between 29si polymerization and
cementitious activity of coal gangue. Journal of Zhejiang University - Science A:
Applied Physics & Engineering 10(9):1334-1340.
Table1. The particle size distribution of CFT.
Cumulative content D10 D25 D50 D75 D90 Average particle size
particle size/μm 1.76 4.59 15.52 46.68 110.2 35.79
10.1680/jadcr.18.00246
Table 2. Chemical and mineralogical composition of materials.
Oxides (mass %) CFT Phase (mass %) CFT

SiO2 40.83 kaolinite 30
Al2O3 14.67 Illite 25
CaO 3.85 Quartz 23
Fe2O3 3.48 Calcite 8
K2O 2.37 Coal 12
SO3 1.53 Other 2
MgO 0.98
TiO2 0.71
Na2O 0.18
P2O5 0.07
Other 0.03
LOI 31.3
Table 3. Influence of calcined CFT with different temperatures on mechanical strength of
cement mortar.
Flexural strength Compressive strength 28d

Temperatures
Samples D90/μm /MPa /MPa activity
/℃
3d 7d 28d 3d 7d 28d index/%
1 700 20.32 4.12 5.75 6.98 19.48 28.13 40.23 78.27
2 750 22.14 5.29 6.25 7.39 22.41 31.84 45.02 87.60
3 800 24.42 4.53 6.53 7.88 23.16 35.65 47.45 92.33
4 850 20.95 4.58 6.96 8.17 23.65 38.10 48.59 94.54
5 900 20.56 5.40 6.37 7.62 23.05 33.46 46.47 90.42
6 950 20.00 4.37 6.12 7.14 19.59 29.98 44.08 85.76
reference cement 5.90 7.51 8.69 32.33 40.46 51.40 100
10.1680/jadcr.18.00246
Table 4. Influence of calcined CFT with different heat preservation times on mechanical
strength of cement mortar.
Heat Flexural strength Compressive strength 28d

Samples preservation D90/μm /MPa /MPa activity
times/h 3d 7d 28d 3d 7d 28d index /%
1 1.0 19.81 2.80 3.63 5.43 13.53 16.02 27.47 53.43
2 1.5 18.18 5.29 7.12 8.56 23.78 39.89 50.64 98.52
3 2.0 20.99 4.58 6.96 8.17 23.65 38.10 48.59 94.54
4 2.5 21.69 4.53 6.08 7.27 22.40 31.45 46.60 90.66
5 3.0 18.57 4.30 5.75 7.07 21.97 30.82 44.81 87.17
Table 5. Influence of calcined CFT with different grinding times on mechanical strength of
cement mortar
Flexural strength Compressive strength

grinding 28d activity
Samples D90/μm /MPa /MPa
times /min index /%
3d 7d 28d 3d 7d 28d
1 20 24.85 4.83 5.97 7.01 22.08 34.46 48.96 95.25
2 30 17.36 5.29 7.12 8.56 23.78 39.89 50.64 98.52
3 40 14.03 5.29 7.30 8.60 24.48 33.42 50.94 99.04
4 60 11.08 5.87 7.31 8.62 25.83 33.58 51.02 99.26
5 120 9.39 5.89 7.42 8.67 27.94 33.03 51.33 99.86
Table 6. Main process and characteristic value of 28d cement paste sample prepared by
different calcination temperatures.
100-400 °C 400-500 °C 650-750 °C

Calcination temperature/°C
weightlessness /% weightlessness /% weightlessness /%
700 6.50 2.18 3.32
750 6.63 1.82 3.59
800 6.86 1.81 3.62
850 7.29 1.79 4.31
900 6.49 1.83 4.20
950 5.67 2.12 4.05
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different heat preservation times.
100-400 °C 400-500 °C 650-750 °C

Heat preservation times/h
weightlessness /% weightlessness /% weightlessness /%
1 6.62 2.06 3.87
1.5 7.84 1.69 4.48
2 7.12 1.71 4.31
2.5 6.82 2.06 3.64
3 6.50 2.07 3.27
different grinding times.
Grinding 100-400 °C 400-500 °C 650-750 °C

times/min weightlessness /% weightlessness /% weightlessness /%
20 7.20 1.83 0.77
30 7.84 1.69 0.99
40 8.36 1.60 1.06
60 8.69 1.42 1.14
120 8.79 1.25 1.32
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Figure captions
Figure 1. The X-ray diffraction (XRD) pattern of Coal Flotation Tailings (CFT).
Figure 2. Thermogravimetric analysis (TGA) combined with thermal gravimetric analysis of
CFT
Figure 3. XRD patterns of calcined CFT at different calcination temperatures.
Figure 4. FTIR spectrum of calcined CFT at different calcination temperatures.
Figure 5. TGA of 28d cement paste made from calcined CFT blended with different
calcination temperatures (a: TG; b: DTG).
Figure 6. TGA of 28d cement paste made from calcined CFT blended with different Heat
preservation times (a: TG; b: DTG)
Figure 7. TGA of 28d cement paste made from calcined CFT blended with different grinding
times (a: TG; b: DTG)
Figure 8. XRD of different hydrated cement paste (1-pure cement paste at 3days; 2-pure
cement paste at 7days; 3 - pure cement paste at 28days; 4-clained products paste at
3days; 5- chained products paste at 7days; 6- chained products paste at 28days)
Figure 9. SEM of pure cement paste and cement paste mixed with calcined samples at 850°C
(maintenance time of cement 3d, 7d and 28d). (a: 3d-pure cement paste; b: 3d-850°C;
c: 7d-pure cement paste; d: 7d-850°C; e:28d- pure cement paste; f:28d-850°C).
10.1680/jadcr.18.00246
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10.1680/jadcr.18.00246

Jadcr.18.00246 Thermal Analysis

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Jadcr.18.00246 Thermal Analysis

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Published online in ‘accepted manuscript’ format: 19 August 2019

Manuscript title: Thermal Activation Mechanism and Pozzolanic Activity Characteristics of

Coal Flotation Tailing

Affiliations: 1School of environment and resources, Southwest University of Science and

Recycling, Ministry of Education, Sichuan Mianyang, China; 3Sichuan Engineering Lab of

Non-metallic Mineral Powder Modification and High-value Utilization, China and

Corresponding author: Yang Huang, School of environment and resources, Southwest

University of Science and Technology Sichuan Mianyang 621010, China. Tel.:

recycling utilization of CFT.

Keywords: Calcined clays; Portland cement; Pozzolans; Thermal analysis

2.1 Raw Materials

2.2 Experiment Methods

3.1Thermal Activation Mechanism

3.2 Pozzolanic activity and hydration mechanism

3.2.1 Mechanical strength test of cement mortar.

Adamiec P, Benezet J. C and Benhassaine A (2008) Pozzolanic reactivity of silico-aluminous

fly ash. Particuology 6(2): 93-98.

Bich C, Ambroise J and Péra J (2009), Influence of degree of dehydroxylation on the

pozzolanic activity of metakaolin. Applied Clay Science 44(3-4):0-200.

& Building Materials 140:293-300.

pozzolanic activity of calcined coal gangue. International Journal of Mineral Processing

Chindaprasirt P, Homwuttiwong S and Sirivivatnanon V (2004) Influence of fly ash fineness

Concrete Research 34(7): 1087-1092.

Du H J and Pang S D (2018) Value-added utilization of marine clay as cement replacement

for sustainable concrete production. Journal of Cleaner Production 198: 867-873.

Escalante-Garcı ´a, A. Fuentes, A. Gorokhovsky et al. (2010) Hydration Products and

Reactivity of Blast‐Furnace Slag Activated by Various Alkalis. Journal of the

American Ceramic Society.2010 (86):2148-2153.

calcined clay minerals: a comparison between kaolinite, illite and montmorillonite.

Cement and Concrete Research 41(1): 113-122.

Fraire-Luna P E, Escalante-Garcia J I and Gorokhovsky A (2006) Composite systems

fluorgypsum–blastfurnance slag–metakaolin, strength and microstructures. Cement and

Concrete Research 36(6): 1048-1055.

Grzegorz G (2017) Generalized fracture toughness and compressive strength of sustainable

concrete including low calcium fly ash. Materials 10(12): 1393.

Hailong W, Xiaoyan S,Junjie W et al.( 2016) Permeability of Concrete with Recycled

Concrete Aggregate and Pozzolanic Materials under Stress. Materials 9: 252.

He C, Makovicky E and Osbæeck B (1994). Thermal stability and pozzolanic activity of

calcined illite. Applied Clay Science 9(3):0-187.

Heikal M (2000) Effect of temperature on the physico-mechanical and mineralogical

clays. Applied Clay Science 132:552-560.

Cement & Concrete Research 38:128-136.

Lafond E, Coumes C C, D Gauffinet S et al. (2017).Solidification of ion exchange resins

slag cement. Journal of Nuclear Materials 483(2017):121-131.

cement-based materials. Journal of Central South University 21(11): 4360-4367.

kaolin. Applied Clay Science 143:159-167.

& Concrete Research 25:332-338.

Marel V D H W and Beutelspacher H (1976) Atlas of infrared spectroscopy of clay minerals

and their admixtures. Engineering Geology 11(2): 156-157.

Papadakis V G, Pedersen E J and Lindgreen H (1999) An AFM-SEM investigation of the

from industrial by-products, as pozzolans of high reactivity. Cement and Concrete

Research 35(10): 1993-1998.

Rodrguezcamacho R E and Uribeafif R (2002) Importance of using the natural pozzolans on

concrete durability. Cement & Concrete Research 32(12): 1851-1858.

Schneider M, Romer M, Tschudin M et al. (2011) Sustainable cement production—present

and future. Cement & Concrete Research 41(7): 642-650.

Schneider NS and Dietmar S (2016) Studying the Hydration of a Retarded Suspension of

Ground Granulated Blast-Furnace Slag after Reactivation. Materials 9: 933.

Concrete Research 25(2):332-338.

Souri A, Golestani-Fard F, Naghizadeh R et al. (2015) An investigation on pozzolanic

Tironi A, Trezza M A, Scian A N et al. (2013). Assessment of pozzolanic activity of different

calcined clays. Cement & Concrete Composites 37(1): 319-327.