Construction and Building Materials 252 (2020) 119130

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Construction and Building Materials

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Potential utilization of copper tailings in the preparation of low heat

cement clinker
Shouwei Jian, Wenbin Gao, Yang Lv ⇑, Hongbo Tan, Xiangguo Li, Baodong Li, Weichao Huang
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, PR China

h i g h l i g h t s

Copper tailings can be used as a raw material for LHC production.

LHC with copper tailings addition showed low hydration heat (72.1 J/g) at 7 d.

The heavy metal leachability of LHC and its paste were much below safe limits.

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

Article history: In order to avoid environmental pollution from copper tailings (CT), this paper presented a study on
Received 2 March 2020 potential utilization of CT in the preparation of low heat cement clinker (LHC). The effect of CT addition
Received in revised form 25 March 2020 on the properties of LHC was investigated by using free lime (f-CaO) content test and X-ray diffraction
Accepted 8 April 2020
(XRD). Furthermore, to study the hydration properties of LHC paste, the produced LHC samples were
mixed with 0.37 wt% gypsum to prepare the LHC paste at a water/binder ratio of 0.30. The compressive
strength, hydration process, hydration products of LHC paste and solidification of heavy metals in LHC
Keywords:
and the hydrated paste were analyzed. The experimental results showed that CT can be used as a raw
Copper tailings
Low heat cement clinker
material for LHC production. The CT is beneficial for the formation of 2CaO
SiO2 (C2S) during the sintering
Hydration properties process of LHC. Furthermore, LHC paste with higher CT addition showed lower hydration heat during the
Solidification first 7 d hydration. With 2 wt% CT added, the hydration of LHC paste can be promoted and the compres-
sive strength was higher than the blank group at the age of 60 d. The leaching tests indicated that heavy
metals in CT can be stabilized in LHC and LHC paste during the sintering process and the hydration
process.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction ground water, introducing a severe threat to the environment

With the rapid development of copper mining industry, a huge
amount of copper tailings (CT) is generated during the flotation
processing of copper ore [1], and the produced CT has brought
about severe environmental problems [2]. According to statistics
[3], more than 30 million tons of CT are discharged annually in
China. As reported [4], the main mineral compositions of CT were
inert minerals such as fayalite (Fe2SiO4), resulting in high density
(3.6–4.0 kg/cm3) and low activity. Lots of CT were treated with
stacking process in the open air, which occupied a large amount
of land resources [1]. Additionally, certain amount of heavy metals
exist in the CT [5], such as Zn, Cr, Ba, Mo, Cu, etc. When the CT suf-
fers heavy rainfall, acid rain or run-off, a large amount of heavy
metals can leach from the CT and migrate to local cropland and
⇑ Corresponding author.
E-mail addresses: yang.lv@whut.edu.cn (Y. Lv), thbwhut@whut.edu.cn (H. Tan).
and human health [6].
According to a previous study [7], CT shows similar chemical
compositions as the normal raw materials used for cement clin-
ker production. Moreover, some of the heavy metals in the CT
have fluxing and mineralization effect on the clinker preparation,
which can improve the burnability of raw meal and increase the
strength of clinker [8,9]. Qiu et al. [7] found that using CT and
coal gangue composite instead of clay could lower the calcina-
tion temperature by 50–100 °C compared with clinker produced
from pure clay raw materials. Besides that, CT incorporation
(1.5–2.5%) can promote the formation of 3CaO
SiO2 (C3S) [8]
and reduce the free lime (f-CaO) content [10]. With the applica-
tion of CT in cement clinker, heavy metal elements in CT have
become an interesting research topic. It has been reported that
the heavy metal elements can enter into mineral phases of
clinker during the sintering process and affect the formation of
mineral phases [11–13].

https://doi.org/10.1016/j.conbuildmat.2020.119130
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 S. Jian et al. / Construction and Building Materials 252 (2020) 119130

These above researches showed that CT can be utilized as a raw

material to produce cement clinker to realize its resource utiliza-
tion. Moreover, the heavy metals in the CT can be solidified in
the cement clinker, thereby achieving the harmless treatment of
the CT and reducing the environmental load of the waste
[7,14,15]. However, due to the presence of fayalite (Fe2SiO4) [16]
and certain amount of heavy metals in CT, the maximum amount
of CT used as cement clinker raw material should not exceed
10%, as described in these literature [7,8].
Many studies mainly focused on the utilization of CT in Ordi-
nary Portland cement clinker (OPC). As reported [17], CT was used
as one of the raw materials for OPC production and the resulted
cement paste has low early age strength. However, as reported
[18], OPC emits a large amount of heat due to hydration, which
may easily result in thermal cracking of mass concrete. In some
cases, such as for the preparation of marine engineering materials,
assembled building materials, nuclear building materials, diversion
tunnel of hydropower station, low heat cement clinker (LHC) was
required [19–21]. It was reported that the partial replacement of
clay by using iron ore tailings can produce LHC and the iron ore
tailings may promote the formation of 2CaO
SiO2 (C2S) [14]. How-
Fig. 1. XRD pattern of CT.
ever, utilization of CT as one ingredient for the preparation of LHC
was rarely reported. The SiO2 (Reagent-grade, AR, 99% purity) and Fe2O3 (Reagent-grade, AR, 99%
Therefore, the aim of this study was to present a systemic inves- purity), coming from Yongda Chemical Reagent Co., Ltd, Tianjin, China, were used to
tigation on potential utilization of copper tailings in the prepara- adjust clinker modulus.
tion of LHC. The influence of CT on the mineral formation of LHC
and its hydration properties was analyzed by chemical analysis, 2.2. Preparation of clinker and paste
X-ray diffraction (XRD), hydration heat and nuclear magnetic reso-
The raw materials were ground to fine powder with particle size less than
nance (NMR). Moreover, the heavy metal content presented in CT
75 lm. Then the powder was dried in an oven at 105 ℃ for 12 h before being used
and the resulted LHC as well as its paste was evaluated with induc- for LHC production. In this study, the LHC samples were prepared with fixed clinker
tive coupled plasma emission spectrometer (ICP). The results modulus, where lime saturation factor (KH), alumina modulus (IM), and silica mod-
would provide a theoretical basis for the utilization of CT in LHC ulus (SM) were controlled to be 0.76, 0.94, and 2.81, respectively [22,23]. The ingre-
and settle the pollution problems of CT. dients design is shown in Table 3. The addition amount of CT varied in the range of
0–6% by mass in the raw meal, with the CT addition of 0%, 2%, 4% and 6% recorded as
LHC0, LHC2, LHC4 and LHC6, respectively.
The raw meal was mixed in a laboratory ball mill for 15 min to ensure that the
2. Materials and test methods
raw meal was mixed well. Then the raw meal mixtures were compressed to form £
50  10 mm cylinders. Afterwards, these cylinders were calcined at 1400 ℃ in a lab-
2.1. Raw materials for LHC
oratory furnace. After being calcined at 1400 ℃ for 60 min, the clinker was cooled
rapidly to room temperature to prevent the formation of c-C2S. The sintered clink-
The limestone, shale and sandstone used in this research were supplied by
ers were ground to powder with the fineness less than 75 lm, being ready for the
Huaxin Cement Co., Ltd. in Hubei province in P.R. China. Copper tailings (CT) were
further characterization.
obtained from Hubei Dajiang Environmental technology Co., Ltd. The chemical com-
In order to investigate the hydration properties of LHC paste, the paste was pre-
positions of limestone, shale, sandstone and CT were obtained by X-ray Fluores-
pared by mixing LHC samples with 0.37 wt% gypsum, and the water/binder ratio of
cence spectrometer (XRF; Zetium-X, PANalytical.B.V, Netherlands), and the results
0.30 was used [24]. The prepared clinker paste was cast into
are presented in Table 1.
20 mm  20 mm  20 mm molds and cured for 24 h at 20 ± 2 °C and relative
In addition, according to results of XRF analysis, the detected heavy metals in CT
humidity exceeding 95%. Afterwards, the LHC paste was demolded and cured in
include ZnO, MoO3, Cr2O3, BaO, TiO2 and CuO, which are the most common heavy
standard curing box till 7 d, 28 d and 60 d for further tests.
metals in the tailings. As the content of above-mentioned heavy metals cannot be
accurately detected by XRF technique, their content was further determined by
means of ICP, as shown in Table 2. 2.3. Test methods
The mineralogical compositions of CT were analyzed by XRD. The crystalline
phases identified by Jade software are presented in Fig. 1. As shown in Fig. 1, the 2.3.1. The free lime (f-CaO) content
main crystalline phases are fayalite (Fe2SiO4), delrioite (ZnS), magnesioferrite The content of f-CaO of grounded cement clinker was analyzed through
(MgFe2O4) and magnetite (Fe3O4). ethanediol-alcohol method according to Chinese standard of GB/T 176–1996 [25].

Table 1
Chemical compositions of raw materials Wt. / %.

LOI SiO2 Al2O3 Fe2O3 CaO MgO SO3 K2O Na2O

Limestone 41.10 4.79 2.14 1.04 48.30 1.06 0.18 0.34 0.11
Shale 7.89 74.10 9.01 4.35 1.18 0.59 0.11 0.71 0.12
Sandstone 9.26 63.60 14.10 6.50 1.25 1.13 0.12 2.01 0.13
CT 2.00 37.40 6.59 36.90 5.25 2.92 1.37 0.61 0.25

Table 2
The content of heavy metals in Copper tailings (mg/kg).

Elements Zn Mo Cr Ba Ti Cu
CT 28925.91 2328.27 2234.65 7231.48 3615.74 693.17
 S. Jian et al. / Construction and Building Materials 252 (2020) 119130 3

Table 3
Ratio of raw materials of samples.

Raw meal Raw materials proportioning: wt. % clinker modulus

Limestone Shale Sandstone Fe2O3 SiO2 CT KH SM IM
LHC0 83.8 6.88 6.01 1.63 1.68 0.00 0.76 2.81 0.94
LHC2 82.6 6.65 5.96 1.22 1.57 2.00 0.76 2.81 0.94
LHC4 81.9 6.05 5.85 0.79 1.41 4.00 0.76 2.81 0.94
LHC6 81.2 5.49 5.66 0.39 1.26 6.00 0.76 2.81 0.94

2.3.2. XRD 3. Results and discussion

The LHC and hydration products of LHC paste were dried and ground to fine
powder with particle size less than 75 lm. Afterwards, the mineral phase of clinkers
and hydration products were conducted by using a D8-Advance X-ray diffractome-
ter (XRD, Bruker Optics, Germany) with CuKa radiation at a voltage of 40 KV and a
current of 40 mA. The two-theta range of overall measurements used was from 5° to
70° in 0.02° steps.
2.3.3. Hydration heat
2.0 g clinker samples were mixed with 0.37 wt% gypsum to prepare clinker
paste. The clinker paste prepared with 2.0 g OPC was used as a reference sample.
The water/cement ration was kept at 0.30. Heat of the paste samples over time were
recorded by an isothermal calorimetry (TAM AIR, C80) at 20 ℃. The evolution of
hydration heat was conducted automatically till the age of 168 h.
2.3.4. NMR analysis
To further explain the hydration of LHC paste, the hydration samples of LHC
were tested by means of 29Si NMR (solid-state nuclear magnetic resonance) tech-
nique. Generally, four peaks can be distinguished in the NMR spectrum of the
hydration samples of LHC, and the hydration degree (a) of cement clinker and
the main chain length (MCL) of calcium silicate hydrate (C-S-H) can be determined
by the relative intensity of these peaks [26]. Q0 means Si-O tetrahedron in the unhy-
drated cement samples; Qn (n = 1, 2) represents the Si-O tetrahedron with different
chain groups in the hydrated samples; Q2 (1 Al) represents middle-chain groups
where one of Si-O tetrahedron is replaced by Al-O tetrahedron in hydration
products.
The analysis of 29Si NMR was obtained by a Bruker Advance III400 spectrometer
at 79.5 MHz, with the rotation frequency of 5 kHz and the delay time of 10 s. The
results were analyzed by X-ray photoelectron spectroscope (XPSPEAK41) software
and the MCL of C-S-H gels and the hydration degree of LHC were calculated as fol-
lows [27]:
   
2I Q 1 þ2I Q 2 þ3I½Q 2 ðAlÞ
MCL ¼ ð1Þ
Q1
IðQ 0 Þ
a ð%Þ ¼ 1  ð2Þ
I0 ðQ 0 Þ
where I (Q0), I (Q1), I (Q2) and I [Q2(1 Al)] denotes the relative intensities of these
peaks in the hydrated samples, respectively; I0 (Q0) represents the integrated inten-
sities of signals for the unhydrated samples.
2.3.5. Compressive strength
The LHC samples were mixed with 0.37 wt% gypsum to prepare LHC paste
according to the standard mixing procedure of ASTM C 305 [28]. The water/binder
ratio of 0.30 was used [24]. The prepared clinker paste was cast into
20 mm  20 mm  20 mm molds, and then cured in the >95% R.H. and 20 ± 2 ℃
chamber for 24 h. Afterwards, the LHC paste samples was demolded and cured to
designated ages of 7 d, 28 d and 60 d. The compressive machine (DYE-300A) was
used to measure compressive strength. Every final value was an average value
obtained from three specimens.
3.1. Characterization of the LHC
3.1.1. f-CaO content of clinker samples
The content of f-CaO is an important indicator in the sintering
process of cement clinker. It directly affects the formation of
3CaO
SiO2 (C3S) and 2CaO
SiO2 (C2S) [30]. The content of f-CaO
in the clinker is given in Table 4.
According to the data in the table, it can be found that f-CaO
content in all clinkers is lower than 0.10%, which meet the require-
ments of LHC standard GB200-2003 [31]. Compared with LHC0,
cement clinkers with CT showed higher f-CaO content with the
increase of CT content from 2% to 6%. This may be due to the sub-
stitution of Ca2+ ions in C2S and C3S by heavy metals (Ba2+, Zn2+,
Cr6+, etc.) in CT during the sintering process of clinker, eventually
leading to slightly increased f-CaO content. The results have been
widely accepted in these literature [32–34].
3.1.2. XRD
The effect of CT on the formation of clinker mineralogical com-
positions was analyzed by XRD. The XRD patterns of LHC and OPC
were plotted in Fig. 2. It can be seen from Fig. 2 (a) that C3S and C2S
are the main mineralogical compositions of LHC and OPC. In addi-
tion, 3CaO
Al2O3 (C3A) and 4CaO
Al2O3
Fe2O3 (C4AF) can also be
seen in XRD patterns. Compared with LHC0, the CT contained sam-
ples showed higher peak intensity of C2S and lower peak intensity
of C3S. The spectrum was magnified in the areas of diffraction
angles 31.34°–33.20° (C3S and C2S), as shown in Fig. 2 (b). As can
be seen from the Fig. 2 (b), these peak positions were shifted to
smaller angle.
Consequently, the main mineralogical phases of LHC with CT
addition were C3S, C2S, C3A, and C4AF, which were in accordance
with the characteristic minerals of the typical cement clinker
[35,36]. The mineralogical compositions combined with the results
of f-CaO content of LHC showed that CT could be utilized as a raw
material for the production of LHC. In addition, the shifts of some
peak positions of C3S and C2S may indicate that the heavy metals
in CT could enter into mineralogical phases of C3S and C2S and
change their crystal structures, in agreement with the results in
the literature [30,37].
3.2. Compressive strength for clinker paste

2.3.6. ICP Fig. 3 shows the compressive strength of LHC paste. As shown in
The heavy metals in CT include Zn, Mo, Cr, Ba, Ti and Cu. Therefore, these heavy
Fig. 3, at the age of 28 d, the compressive strength of LHC0, LHC2,
metals in CT were measured by Inductively Coupled Plasma-Optical Emission Spec-
trometer (ICP, Prodigy 7, LEEMAN LABS INC, USA). LHC4 and LHC6 is 44. 1 MPa, 18.6 MPa, 11.3 MPa and 5.7 MPa,
respectively. After 60 d hydration, the compressive strength of
2.3.7. Leaching tests LHC2 was significantly improved, even higher than that of LHC0.
Heavy metals, including Zn, Mo, Cr, Ba, Ti and Cu, in CT, clinkers and hydration However, the compressive strength of LHC6 was still very low.
products were extracted according to Chinese National standard of HJ/T299-2007
[29]. An extraction fluid with an initial pH of 3.20 ± 0.05 was prepared by adding Table 4
a mixture HNO3 and H2SO4 (m(HNO3):m(H2SO4) = 1/2) to deionized water. The liq- CaO cement of clinker samples (wt%).
uid/solid ratio was maintained at 10/1 (L/kg). The samples were broken into small
pieces with a particle size of less than 9.5 mm and tumbled at 30 ± 2 rpm for Sample LHC0 LHC2 LHC4 LHC6
18 ± 2 h. The concentration of heavy metals in the leachate was obtained by using f-CaO 0.04 0.05 0.06 0.08
ICP.
4 S. Jian et al. / Construction and Building Materials 252 (2020) 119130
Fig. 2. XRD patterns of Cement clinker.
Fig. 3. Compressive strength of LHC for 28 d and 60 d.
The development of strength of LHC paste was mainly provided
by C3S hydration at 28 d [38]. However, the hydration rate of C2S
was very slow, about 1/20 of that of C3S. The peak intensity of
C3S in the clinker of LHC2, LHC4 and LHC6 decreased as the amount
of CT increased, as shown in our results. Moreover, Zn in the clinker
may inhibit hydration of C3S at 28 d [13,37]. The results indicated
that CT may inhibit the hydration of cement clinker before 28 d,
resulting in decreased compressive strength of 28 d. At the later
stage, the development of compressive strength was mainly pro-
vided by C2S hydration. Ba2+, Cr3+ and Cr6+ in CT may enter into
C2S during the sintering process [11,37], and thus increase the
activity of C2S and promote hydration reaction of C2S. Eventually,
the compressive strength of LHC2 and LHC4 at 60 d was greatly
increased. However, the strength of LHC6 for 60 d with 6% CT paste
was still very low. This was mainly due to the formation of a large
amount of AFm in the hydration products of LHC6 at the early per-
iod, which can be observed in Fig. 5. The layer structured AFm was
attached on the unhydrated LHC particles, resulting in the retarda-
tion of the hydration of LHC. This phenomenon had been described
in the previous literature [39].
3.3. Hydration properties of LHC
3.3.1. Hydration heat
Fig. 4 shows the evolution of hydration heat of LHC paste sam-
ples. Generally, after being mixed with water, C3A reacts immedi-
ately, and then is followed by C3S and C4AF. The hydration rate of
C2S is relatively slow, about 1/20 of that of C3S [40,41].
As shown in Fig. 4 (a), compared with OPC, the main exothermic
peak of LHC was delayed and reduced greatly. In addition, it is
noticed that bimodal phenomenon appears in the hydration rate
curve of LHC. This could be explained that because there was more
C2S than C3S in LHC, then the surface of C3S particles was wrapped
by the C2S particles. In addition, the surface of the C3S could be fur-
ther surrounded by the hydration products of C3A. It was equivalent
to forming a ‘‘protective film” around C3S, which could delay the
hydration of C3S [42]. When water molecules diffuse through this
‘‘protective film”, the first exothermic peak appeared on the curve
of hydration reaction. Then hydration products crystallized and
grew in a certain direction in space, breaking through the ‘‘protec-
tive film” of C3S to form a channel [43]. In this case, water molecules
were easily contacted with C3S to form the second exothermic peak
of C3S. As can be seen clearly from Fig. 4 (a), with the increase of CT
content in clinker raw meal, the induction period of the hydration
was gradually prolonged and the time span of acceleration period
and deceleration period was increased. Meanwhile, the main
exothermic peak of C3S gradually dropped as the increase of CT con-
tent. As reported, Zn from CT may enter into the clinker mineral
phases in the sintering process of clinker. Moreover, Zn2+ ions
may retard the early hydration of C3S and prolong the hydration
period, in agreement with the results in the literature [13,37].
The accumulated hydration heat of OPC and LHC is presented in
Fig. 4 (b), which shows that the accumulated hydration heat of LHC
was significantly lower than that of OPC. Furthermore, the accu-
mulated hydration heat of LHC with CT addition (2–6%) was lower
than 72.1 J/g at the age of 7 d, which meet the requirements of LHC
standard GB 200–2003 [31]. The cement clinker with CT showed a
lower accumulated hydration heat compared with reference
(LHC0). In addition, as the amount of CT increased in clinker raw
meal, the hydration heat of the LHC was gradually decreased. These
results indicated that CT may reduce the hydration heat of LHC.
3.3.2. XRD
Fig. 5 presents the XRD patterns of LHC paste hydrated for 28 d
and 60 d. As reported [44,45], calcium hydroxide (CH), ettringite
 S. Jian et al. / Construction and Building Materials 252 (2020) 119130 5

Fig. 4. Hydration heat of OPC and LHC.

Fig. 5. XRD patterns of LHC paste hydrated for 28 d and 60 d.

(AFt), monosulfate (AFm) and calcium silicate hydrate (C-S-H) are
the most common hydration products of cement clinker. However,
due to the poor crystallinity of the C-S-H gels, its presence is diffi-
cult to be identified in the XRD patterns. As observed in Fig. 5 (a),
compared with LHC0, the peak of CH is low for LHC2, LHC4 and
LHC6. The peaks for the unhydrated C2S were very obvious. In addi-
tion to AFt in LHC2, LHC4 and LHC6, AFm was formed in the hydra-
tion products. For LHC4 and LHC6, AFm was the main hydration
product at 28 d. The cement clinker with CT has higher peak inten-
sity of C2S. However, the reaction rate of C2S is extremely slow.
Therefore, a large amount of unhydrated C2S were remained at
the early period of hydration. In addition, Mo and Ti in CT may
enter into C3A and C4AF in the sintering process [12]. Mo and Ti
may affect hydration of C3A and C4AF to hasten the conversion of
AFt to AFm, in agreement with the results in the literature
[12,39]. With the increase of CT content in raw materials of LHC,
there was more AFm in hydration products of LHC.
Furthermore, at the age of 60 d, as noted in Fig. 5 (b), the peak
intensity of CH for LHC2 and LHC4 paste was increased signifi-
cantly. For LHC0 and LHC6, the change was not obvious. These find-
ings from XRD indicated that appropriate amount of CT can
promote the hydration of LHC at the late period.
3.3.3. 29Si NMR analysis
The deconvoluted 29Si NMR spectra of the hydrated samples for
28 d is presented in Fig. 6. The calculated hydration degrees of LHC
and MCL of C-S-H are listed in Table 5. From Fig. 6, Q0, Q1, Q2, Q2
(1 Al) can be obviously seen in LHC0. LHC2, LHC4 and LHC6 samples
showed much lower intensity of peaks associated with the Q1, Q2
and Q2 (1 Al). In the case of LHC6, the Q2 (1Al) peak was barely
detected.
Additionally, the Q0 peak intensity is higher in Fig. 6 (b), Fig. 6
(c) and Fig. 6 (d) compared to Fig. 6 (a). These results indicated that
there are more unhydrated silicate phases in LHC2, LHC4 and LHC6.
More details can be found in Table 5. After 28 d of hydration, the
hydration degree of LHC0 was 34.89%, the MCL of the resulting C-
S-H gels was 4.38; the hydration degree of LHC2 was only 9.87%,
producing C-S-H gels with an MCL of 3.62; the hydration degrees
of LHC4 and LHC6 were 7.59% and 4.88%, respectively. These results
demonstrated that CT would inhibit the hydration of the silicate
phases and reduced the polymerization degree of the C-S-H gels
at the age of 28 d hydration.
To further study the effect of CT on the later hydration of LHC,
the deconvoluted 29Si MAS NMR spectra for the hydrated samples
at 60 d is plotted in Fig. 7. The calculated hydration degrees of LHC
and MCL of the produced C-S-H are listed in Table 6. From Fig. 7,
Q0, Q1, Q2 and Q2 (1Al) can be seen clearly. After 60 d hydration,
signal intensity of Q1, Q2 and Q2(1Al) obviously increased, which
shows that more C-S-H gels were produced in the LHC paste. In
comparison with LHC0, Q0 peak intensity decreases and Q2 peak
intensity increases in LHC2 at the age of 60 d. However, peak inten-
sities of Q1, Q2 and Q2 (1 Al) were still weak for the LHC6. As can be
6 S. Jian et al. / Construction and Building Materials 252 (2020) 119130

29
Fig. 6. Deconvolution of the Si NMR spectrum at 28 d.

Table 5
Deconvolution results of the sample at 28d.

Q0 (%) Q1 (%) Q2 (%) Q2 (Al) (%) a (%) MCL

LHC0 65.11 17.80 9.03 8.07 34.89 4.38
LHC2 90.13 5.99 2.19 1.77 9.87 3.62
LHC4 92.41 4.80 1.10 0.56 7.59 2.81
LHC6 95.12 4.35 0.61 0.00 4.88 2.28

seen from the Table 6, after 60 d of hydration, the hydration degree
of LHC2 was higher than that of LHC0. Meanwhile, MCL in the C-S-H
gel of LHC2 (4.98) was longer than that of LHC0 (4.66). The hydra-
tion degree of LHC4 is 37.72%, forming C-S-H gels with an MCL of
4.27. However, the hydration degree of LHC6 was still very low,
with the hydration degree of only 23.26% at the age of 60 d.
It can be concluded that the hydration of LHC with CT incorpo-
ration of 2% was inhibited at early age, but significantly accelerated
at late age. In addition, an appropriate amount of CT may promote
the conversion of C-S-H gels from an oligomeric state to a high
polymorphic state at the age of 60 d [11,46].
3.4. Solidification of heavy metals
Table 7 presents the leaching contents of heavy metals in CT,
LHC and its hydration products. The results illustrate that the
leaching contents in LHC are much lower compared to CT. Addi-
tionally, as the hydration progressed, the leaching contents of
heavy metals were reduced gradually. After hydration for 60 d,
there is almost no heavy metals in hydration products.
As a consequence, heavy metals in CT were solidified in the
mineral phases during the sintering process of clinker. In addi-
tion, heavy metals can be solidified by hydration products. As
reported [12,39], during the formation of AFm, Al3+ in AFm
can be replaced with free Mo5+ and Ti4+. C-S-H has extremely
high specific surface energy and ion exchange capacity. It can
control a variety of metal cation movements through physical
adsorption and interlayer chemical replacement [47]. Therefore,
most heavy metal ions (Zn2+, Ba2+, Cu2+ and Cr6+) can enter into
the middle of the C-S-H interlayer. The results showed that
leaching contents of different heavy metals were below the
regulatory limits (Zn, Cu, Ba: 100 mg/L; Ti, Mo: 5 mg/L;
Cr: 15 mg/L). Therefore, it is safe that CT is used as partial
raw materials to produce LHC.
 S. Jian et al. / Construction and Building Materials 252 (2020) 119130 7

29
Fig. 7. Deconvolution of the Si NMR spectrum at 60 d.

Table 6
Deconvolution results of the sample at 60 d.

Q0 (%) Q1 (%) Q2 (%) Q2 (Al) (%) a (%) MCL

LHC0 41.18 28.00 17.73 13.09 58.82 4.66
LHC2 37.94 27.50 21.72 12.84 62.06 4.98
LHC4 62.28 16.85 6.35 8.52 37.72 4.27
LHC6 76.74 14.97 5.87 2.42 23.26 3.26

Table 7
Leaching contents of different heavy metals in samples (mg/L).

Samples Zn Ba Ti Mo Cr Cu
CT 4.268 3.151 2.820 4.182 2.391 0.101
LHC2 0.014 0.013 0.548 0.456 0.378 0.011
LHC2 28 d 0.010 0.011 0.018 0.053 0.014 0.003
LHC2 60 d N N N N N N
GB5085.3-2007 [48] 100 100 5 5 15 100

N: Below detection limit.

4. Conclusions
The research presented a synthetical investigation on the
potential utilization of copper tailings in the preparation of LHC.
The clinker phases, f-CaO contents in clinkers, compressive
strength, hydration heat, hydration products, and solidification of
heavy metals in clinker and its pastes were analyzed. The main
conclusions can be drawn as follows:
(1) The CT can be used as a raw material for LHC production. The
LHC produced with CT addition present lower hydration
heat than that of LHC without CT addition. The accumulated
hydration heat of LHC with CT addition (2–6%) was below
72.1 J/g at the age of 7 d.
(2) 29Si NMR analysis and XRD analysis of hydration products
showed that CT may inhibit the hydration of LHC at the
age of 28 d. However, appropriate amount of CT may
8 S. Jian et al. / Construction and Building Materials 252 (2020) 119130
promote the hydration of C2S, facilitating the formation of C-
S-H. Furthermore, the compressive strength of LHC with 2%
CT addition was 71.5 MPa which was higher than the com-
pressive strength of LHC without CT addition at the age of
60 d.
(3) Leaching contents of heavy metals in clinkers and paste
samples were much below the regulatory limits
(GB5085.3–2007), indicating that the heavy metals in CT
can be stabilized in the LHC and LHC paste.
The research results would provide a theoretical basis for the
resource reutilization of CT in LHC production and contribute to
the diminished environmental issue relating to the safety manage-
ment of CT.
CRediT authorship contribution statement
Shouwei Jian: Conceptualization, Validation, Resources, Fund-
ing acquisition, Project administration. Wenbin Gao: Conceptual-
ization, Methodology, Software, Formal analysis, Investigation,
Data curation, Writing - original draft. Yang Lv: Conceptualization,
Formal analysis, Writing - review & editing. Hongbo Tan: Investi-
gation, Resources. Xiangguo Li: Validation, Methodology. Baodong
Li: Resources, Investigation, Validation, Supervision. Weichao
Huang: Methodology, Software, Formal analysis.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was supported by National Key Research and Devel-
opment Program of China (2017YFC0703202) and China Postdoc-
toral Science Foundation (2018M640739). The authors would like
to thank the State Key Laboratory and Center for Materials
Research, Wuhan University of Technology, for material
characterization.
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