Development of A New Supplementary Cementitious Material From The PDF
Development of A New Supplementary Cementitious Material From The PDF
Development of A New Supplementary Cementitious Material From The PDF
a r t i c l e i n f o a b s t r a c t
Article history: The use of tailings as aggregate and supplementary cementitious materials has been studied previously.
Available online 3 February 2018 Nevertheless, tailings are generally used as collected, without treatment, showing low cementitious
capacity allowing low replacement levels of cement (below 15%). This research studies eight copper
Keywords: tailings to determine which tailings are likely to improve their cementitious capacity as supplementary
Tailing cementitious material by using thermal and mechanical treatments. In the first stage, using TGA and PSD,
Heat treatments
the capacity of the tailings to undergo chemical transformations through a thermal treatment of up to
Mechanical treatments
1000 C and physical transformation through low-energy milling for up to 180 min, were explored.
Relevant chemical modifications were observed over the range of 500 Ce900 C, with peaks between
600 C and 800 C. It was also observed that due to the nature of rock processing prior to mineral
extraction, the particle size was able to be reduced by 50% after 60 min of milling or less. With these
results, a central composite design was proposed using thermal treatment temperatures between 600 C
and 800 C (central point at 700 C) and milling with a central point at 30 min. The results show that the
mechanical performance of the mixtures can be improved by up to 40% at 90 days compared to untreated
tailings at a 40% replacement level.
© 2018 Elsevier Ltd. All rights reserved.
1. Introduction 2009), phosphates (Zheng et al., 2015), iron (Zhao et al., 2014),
and copper (Onuaguluchi and Eren, 2012) both as SCM and as a fine
The impact of cement production on the environment is one of aggregate.
the main factors in the search for new materials and construction The copper mining industry is one of the most important
methods. The production of 1 metric ton of Portland cement in- extractive industries worldwide, with production levels of
volves the emission of nearly 1 t of CO2 to the atmosphere: approximately 19.4 million t in 2016 (U.S. Geological Survey, 2017).
approximately 50% comes from the decomposition of carbonates Each ton of refined copper generates 196.5 tons of tailing
(Schneider et al., 2011). Globally, clinker production accounts for 5% (Onuaguluchi and Eren, 2012) andddepending on the technique
of total CO2 emissions (Ludwig and Zhang, 2015). Supplementary applied, which is associated with the type of rockdbetween 2.2
cementitious materials (SCM) have been used to replace part of the and 3 t of copper slag (Shi et al., 2008). The tailings are a mixture of
cement (Schneider et al., 2011) to reduce the impact of the pro- by-products generated from the extraction process from the ores
duction of cement. In recent developments, the use of tailings as using mineral and hydrometallurgical processes (Wang et al., 2014),
SCM has been studied: the use of tungsten tailings (Choi et al., specifically when the crushed rock enters the separation process
performed by floating of the “copper concentrate”, in which the
fraction of high copper concentrations (30% by mass) is further
* Corresponding author. Department of Construction Engineering and Manage- processed, and the rest is discarded as tailing (Davenport et al.,
ment, School of Engineering, Pontificia Universidad Catolica de Chile, Vicuna 2002).
Mackenna 4860, Chile.
The use of copper tailings has been researched both as SCM with
** Corresponding author.
E-mail addresses: [email protected] (F. Vargas), [email protected] (M. Lopez).
Portland cement (Deng et al., 2014; Onuaguluchi and Eren, 2015,
https://doi.org/10.1016/j.jclepro.2018.01.223
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
428 F. Vargas, M. Lopez / Journal of Cleaner Production 182 (2018) 427e436
2013, 2012; Thomas et al., 2013a) and as a fine aggregate replace- milling. The combined effect of different treatments has also been
ment (Zhang et al., 2014). Copper tailings have also been investi- documented for some pozzolanic and non-pozzolanic materials
gated as a principal element in the production of bricks through a (Jain, 2012).
geopolymerization process (Ahmari and Zhang, 2012). In blends The aim of this research was to scientifically define promising
with Portland cement and tailings, one study (Onuaguluchi and treatments to maximize the cementitious activity of copper tailings
Eren, 2012) indicated that at replacement levels of 10% by mass, to enable their feasible use as SCM in concrete. Therefore, a first
concrete strength exceeds the normal performance by 16.2% over stage was developed on tailings to observe their performance as
28 days. However, it has been demonstrated that with higher SCM as found without any treatment. The optimal temperatures
replacement levels (until 20%), there is no sizable impact or even and the appropriate grinding time needed to obtain changes in
loss in compressive strength over 28 days up to 15% (Zhang et al., particle size were then determined. Finally, a central composite
2014). factorial design was used to observe the effect of each treatment
The effect of the use of any SCM in concrete can be divided into separately and in combination on selected tailings.
two contributions occurring simultaneously (Juenger and Siddique,
2015; Thomas, 2013): 2. Materials and methods
a Chemical contribution: also called the pozzolanic effect, related Eight samples of tailings were collected from different sources
to the reaction and hydration products of portlandite and in Chile and used in this study in a first exploratory stage. Six of the
aluminosilicate phases present in the SCM's (Lothenbach et al., tailings came from long-standing tailings (LS) in Copiapo, Chile and
2011). two from ongoing production (OP) mines in Salamanca and Til-Til,
b Physical contribution: also called the filler effect, related to the Chile. Among the eight original tailings, three were selected to
space between particles and the surface in the hydration assess the effect of the treatments in their performance as
products (Lothenbach et al., 2011) which can be separated from supplementary cementitious materials. The tailings were collected
the chemical effect (Zunino and Lopez, 2016). by means of sampling in at least three locations of the deposit and
then homogenized by mixing them in one representative sample of
Considering both effects and the poor performance shown by 40 kg. For this research, only the fraction of tailing passing through
copper tailings as SCM at higher replacement levels (Thomas et al., a No. 30 sieve (600 mm) was considered; i.e., the larger particles
2013b; Zhang et al., 2014), activation stands as an alternative to (approximately 15%) were discarded. For the experimental program
transformation into a more attractive cementing material (Peng conducted, type I OPC was used.
et al., 2015). The improvement of performance in supplementary
cementitious materials has been researched since the mid-20th 2.1. Chemical characterization
century, with the use of thermal treatments. Optimal tempera-
tures for chemical and mineralogical changes with the potential to The chemical composition of the tailings was determined by
improve the chemical effect of SCM are 800 for andesite (Hamidi X-ray fluorescence (XRF), using a Bruker S8 Tiger spectrometer, and
et al., 2013) and 650e700 for kaolinite and kaolinite-bentonite the results are shown on Table 1. The specific gravity (SG) of the raw
(Souri et al., 2015; Taylor-Lange et al., 2015). However, other SCM materials is included in the table.
show lower improvements with calcination: zeolites have been The mineralogy composition of the tailings was determined by
researched with temperatures above 300 without showing great qualitative X-ray diffraction (XRD), using a Miniflex diffractometer
pozzolanic capacity after the treatment, and changes are more of 30 kV, 10 Maq; Rigaku with a Cu Ka source. The diffractograms
closely related due to morphology and particle size than chemical were recorded between angles 2q ¼ 5 and 40 with a scan rate of
contribution (Kuçukyıldırım and Uzal, 2014; Seraj et al., 2016). 2 /min at room temperature.
Changes in particle size also have been researched for SCM as an
effective method to improve performance, generally with high- 2.1.1. Thermogravimetric analyses (TGA)
energy methods (Burgos et al., 2014; Fuentes et al., 2014). The Simultaneous thermal gravimetric analysis (TGA) and differen-
combined effect of thermal and milling treatments has increased tial scanning calorimetry (DSC) were performed on the eight
effectiveness, with particle size above 45 mm (Hamidi et al., 2013; untreated tailings to understand how thermal treatment affects
Tironi et al., 2013). Treatments without high-temperature pro- phase decomposition and to determine the best treatment tem-
cesses also show improvements in the reactivity of zeolites (Burris perature. The TGA/DSC tests were performed on crushed samples,
and Juenger, 2016) and kaolin (Ilic et al., 2016) when combined with passed through a No. 200 sieve (75 mm opening), using a TA
Table 1
Chemical composition of OPC and tailings. Chemical composition data are presented as oxide percentage by weight.
Percentage of Oxides (%) OPC OP1 OP2 LS1 LS2 LS3 LS4 LS5 LS6
SiO2 20.3% 62.90% 59.90% 49.40% 60.20% 51.90% 73.70% 42.60% 31.8%
Al2O3 4.9% 9.50% 16.90% 10.30% 12.20% 16.70% 5.40% 8.80% 6.9%
Fe2O 3.1% 12.60% 2.80% 18.70% 7.00% 10.60% 12.50% 11.00% 37.9%
CaO 63.0% 2.80% 2.70% 5.10% 5.90% 4.40% 1.80% 12.70% 8.6%
MgO 0.3% 1.10% 1.90% 2.70% 1.70% 3.80% 0.50% 2.50% 2.4%
SO3 2.5% 0.70% 1.30% 2.60% 1.40% 0.40% 0.40% 1.80% 0.1%
Na2O 0.2% 1.30% 3.20% 1.30% 2.30% 3.80% 0.50% 1.60% 2.7%
K2O 0.8% 3.30% 4.10% 2.60% 2.60% 2.90% 1.30% 1.80% 1.8%
TiO2 0.4% 0.20% 0.70% 0.50% 0.70% 1.10% 0.40% 0.40% 0.5%
P2O5 0.1% 0.10% 0.30% 0.20% 0.30% 0.40% 0.10% 0.10% 0.1%
MnO 0.1% 0.10% <LOD 0.20% 0.10% 0.30% 0.10% 0.70% 0.20%
CuO <LOD 0.70% 1.00% 0.30% 0.80% 0.70% 0.40% 0.20% 0.30%
LOI 2.3% 4.40% 5.30% 5.80% 4.20% 2.80% 3.00% 14.50% 6.4%
Specific Gravity 3.124 3.01 2.992 2.925 2.79 2.778 2.887 2.864 3.211
F. Vargas, M. Lopez / Journal of Cleaner Production 182 (2018) 427e436 429
Instruments TGA/DSC Q600. During the test, the chamber gas used plastic containers until the date of mixture.
was nitrogen at a 50 mL/min flow. The samples were stabilized in
alumina crucibles at 30 C for 10 min and then heated from 30 C to 2.5. Isothermal calorimetry
1000 C at a rate of 20 C/min.
Isothermal calorimetry tests were conducted to assess the effect
2.2. Physical characterization of the treatments at the central point and compare it with the
untreated tailings, analysing only the pozzolanic capacity of the
Particle size distributions (PSD) of the eight tailings and OPC tailings. The measurements were taken using a TAM Air isothermal
were measured using a Malvern Mastersizer 2000 laser diffrac- calorimeter using the procedure proposed previously (Avet et al.,
tometer. Isopropanol (refractive index 1.378) was used as a 2016; Snellings and Scrivener, 2015) at 20 C, in mixes with por-
dispersant, and the PSD was measured for 12 s five times while tlandite and calcium sulphate (LC3-50 system), with single
stirring at 2000 rpm to obtain an average measurement. The PSD replication.
results for the untreated tailings are shown on Fig. 1. For the SEM
images, samples were dried and gold-coated. Magnifications be- 3. Exploration of factors: results and discussion
tween 300 and 5000 with an accelerating voltage of 15 kV were
used. In this stage, an exploratory procedure was developed to obtain
a relevant experimental region of interest for the activation stage
2.3. Tailing strength development and the experimental design.
The first step was a review of the compressive strength of paste
Mixture proportioning was designed by mass to avoid the effect mixes of untreated tailing at 7, 28 and 90 days, at a replacement
of volume changes due to thermal and mechanical treatments. The levels of 20%, 40% and 50% by mass.
water-to-cementitious (w/c) materials ratio of the pastes was fixed The second analysis was related to the use of TGA/DSC curves to
at 0.5 by mass. Three 100% OPC mixtures were selected as refer- obtain a range of temperatures in which chemical changes on
ences, with w/c ratios of 0.5, 0.55 and 0.6. The samples were tested tailings could be observed. With these results, and the analysis of
at 7, 28 and 90 days. the XRD patterns, the potential of the tailings as a supplementary
cementing material could be assessed. With the result of this step,
2.4. Treatment on tailings three tailings were selected considering the potential capacity of
tailings as supplementary cementitious material and their origin, so
The treatments in tailings were performed according to the recent and long-standing tailings were evaluated. The final three
following procedure: first, the tailings in batches of 200 g were tailings were used in a third analysis, which was related to the
introduced in the mill. For the milling procedure, a rotational mill particle size changes due to different milling times. The mill was
was chosen, similar to the conditions present in mills currently operated at 40 rpm, with samples milled for 15, 30, 60, 90, 120, 150
used to grind other SCMs, since this type of milling would be more and 180 min.
feasible to implement in an industrial environment. The thermal
treatment on the tailings was then performed in the same batch of 3.1. Compressive strength
200 g using a programmable Nabertherm HT 40/16 electric muffle
oven. The heating cycle started at room temperature and proceeded The results of the untreated tailings pastes are shown in Fig. 2. It
at 10 C/min to the maximum temperature indicated by the can be seen that depending on the tailing, the results vary widely.
experimental program. The maximum temperature was stabilized All tailings exhibit lower strength ratios than the OPC paste at the
for 20 min, and then the oven was left to cool to room temperature same w/c ratio, the expected result considering the replacement
at a free rate. The resulting calcined tailings were stored in sealed (Onuaguluchi and Eren, 2013, 2012; Thomas et al., 2013b).
0,9
20% 40% 50%
0,8 W/C 0.55
0,5
0,4
0,3
W/C 1
0,1
0
OP1 OP2 LS1 LS2 LS3 LS4 LS5 LS6
0,9
20% 40% 50%
0,8
W/C 0.55
0,7
Rtailing/RPC 28 days
W/C 0.6
0,6
W/C 0.625
0,5
0,4
0,3
0,1 W/C 1
0
OP1 OP2 LS1 LS2 LS3 LS4 LS5 LS6
0,9
20% 40% 50%
W/C 0.55
0,8
W/C 0.625
0,6
0,5
0,4
0,3
W/C 0.833
0,2
W/C 1
0,1
0
OP1 OP2 LS1 LS2 LS3 LS4 LS5 LS6
Fig. 2. Compressive strength ratios (referenced to the 100% OPC mixture) versus tailing mixtures at 7, 28 and 90 days for 20%, 40% and 50% replacement levels.
Specifically, reductions in compressive strength between 20% and between OPC paste at w/c of 0.4 and the pastes with tailings tend to
80% were obtained depending on the tailing and replacement level. decrease, which is attributable to the presence of phases capable of
This shows that the base cementitious capacity of the tailings generating pozzolanic reactions in the tailings (Aïtcin, 2016;
can vary importantly. At later ages, the gap in compressive strength Lothenbach et al., 2011).
F. Vargas, M. Lopez / Journal of Cleaner Production 182 (2018) 427e436 431
If the comparison is made against OPC pastes considering only carbonate minerals such as calcite and dolomite (Cao et al., 2016;
the cement reductiondi.e., an increase to a new w/c ratio (dashed Hamidi et al., 2013). In the case of tailings LS1, LS2 and LS5, this
lines)dthe improvement in compressive strength is important. mass loss is between 2% and 6%. With these results, the chosen
This means that the use of raw tailings in addition to the cement, tailings were OP1, LS1 (from the previous step) and LS5. As the
instead of replacing cement, improves compressive strength results show major mass loss at temperatures between 500 C and
significantly. For example, tailings OP1, OP2, LS2 and LS3 show 800 C, the experimental space of interest was chosen between
important increases in compressive strengths in the analysis 600 C and 800 C, centred at 700 C. At these temperatures, major
compared to their respective dash lines. improvement is expected in the performance of the tailings as SCM.
For the next stage, mixtures with a 40% replacement level will The XRD patterns (Figs. 4e6) show similar results to TGA, with
be used to assess the improvements due to the treatments more the previous selected temperatures of thermal treatment. First, the
precisely. In addition, tailings OP1 and LS1 were selected due to high crystallinity of the minerals of the tailings was reported pre-
their performance and their difference in precedence (one is from viously, with the presence of kaolin, calcite and dolomites, due to
an ongoing production mine, and the other is from a long-standing the nature of the rock from which copper is extracted in Chile
tailing). (Smuda et al., 2014, 2008). Second, it can be seen that at 600 C, the
kaolin phase peaks disappear due to the change into amorphous
phases (Hamidi et al., 2013; Taylor-Lange et al., 2015). At 800 C,
3.2. Temperature: TGA-DSC and XRD pattern finally, the calcite and dolomite peaks disappear due to dehy-
droxylation of these phases (Hamidi et al., 2013). The presence of
TGA-DSC results obtained for all tailing samples are shown in
Fig. 3. The results show the differences between the tailings
regardless of the similarities in chemical composition. Neverthe-
less, there are some common peaks in mass loss and endothermic
peaks. After the mass loss due to water content below 150 C, the
first mass loss and endothermic peak, between 400 C and 640 C,
is related to the transformations of kaolinic phases present in the
tailings, due to dehydroxylation and the loss of hydroxyl groups
(Cao et al., 2016; Hamidi et al., 2013; Taylor-Lange et al., 2015). Due
to the low amount on the mass loss (below 3%), it is expected that
the pozzolanic activity of the tailings will be low (Teklay et al.,
2014). The second endothermic peak and mass loss is centred at
750 C. This temperature is related to the decarbonation of
Fig. 4. XRD Pattern of OP1 tailing, untreated and calcined at 600, 700 and 800 C (Q:
quartz; Cr: cristobalite; Z: zinc oxide (i.s.); F: feldspar).
Fig. 3. Thermogravimetric curve (TGA) and differential scanning calorimetry (DSC) Fig. 5. XRD pattern of LS1 tailing, untreated and calcined at 600, 700 and 800 C (Q:
curves of 8 tailings. quartz; Cr: cristobalite; A: anorthite; Z: zinc oxide (i.s.); F: feldspar).
432 F. Vargas, M. Lopez / Journal of Cleaner Production 182 (2018) 427e436
Fig. 6. XRD pattern of LS5 tailing, untreated and calcined at 600, 700 and 800 C (Q:
quartz; a: albite; Z: zinc oxide (i.s); F: feldspar).
In Fig. 1, it is observed that the PSD of untreated tailings has milling treatments such as those subjected to the mineralogical
values comparable to those of other supplementary cementitious process. In image number 3 (LS5 tailing), the presence of micro-
materials (Thomas, 2013). The results of the exploratory milling fractures that facilitate the milling process of the tailings has been
process of 3 tailings can be seen in Fig. 7. There is a significant emphasized.
decrease in particle size in the first 60 min of milling for the old
tailings. In the case of mine tailings in production, the reduction is 3.4. Experimental design for treated tailing pastes
smaller because the particle size is already small when the process
is started. Due to the differences in the rock process and the For the next stage, the results of the exploration of factors were
development of the mine production, the particle size of the tail- considered to obtain an experimental region of interest. The chosen
ings has been reduced to optimize the extraction of copper from the replacement level was 40% by mass. The range of temperature
ores for newer productions (Davenport et al., 2002). The results considered for the thermal treatment was centred at 700 ± 100 .
show that with 60 min max. Milling, the particle size decrease is The base range of time for the milling treatment was centred at
important. The times chosen for the next step were centred at 30 min ± 21.22 min. A second-order model of response surface
30 min. called central composite design for two factors is proposed, which
In Fig. 8, the SEM images shows the morphology of the tailing allows high levels of rotatability of factors. The model considers a
particles, which follow the characteristic pattern of particles from significance level of 95%. Another advantage of the chosen
Fig. 7. Particle size fraction d(0.9) and d(0.5) of 3 tailings after grinding.
F. Vargas, M. Lopez / Journal of Cleaner Production 182 (2018) 427e436 433
Table 3
Compressive strength ratios (referenced to the same tailing without treatment) versus mixtures at 7 and 90 days of age, 40% replacement level.
Table 4
Estimates and significance of coded estimates on regression models for treatments on tailings, at 95% significance level, for 7 and 90 days. Boldface indicates
estimates that are statistically significant.
5. Conclusions
MgO and other possible phases generated by the treatments, performance and socioeconomic implications for the Lefke-Xeros area of
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ductiondpresent and future. Cement Concr. Res. 41, 642e650. https://doi.org/
1150251 and the doctoral scholarships CONICYT-PCHA/Doctorado 10.1016/j.cemconres.2011.03.019.
Nacional/2015e21150946 as well as by CEDEUS, CONICYT/FON- Seraj, S., Ferron, R.D., Juenger, M.C.G., 2016. Calcining natural zeolites to improve
DAP 15110020. The testing performed in this study was mainly their effect on cementitious mixture workability. Cement Concr. Res. 85,
102e110. https://doi.org/10.1016/j.cemconres.2016.04.002.
conducted at the Construction Materials Laboratories at Pontificia Shi, C., Meyer, C., Behnood, A., 2008. Utilization of copper slag in cement and
Universidad Catolica de Chile, Dictuc Laboratories in Chile, and in concrete. Resour. Conserv. Recycl. 52, 1115e1120. https://doi.org/10.1016/
the Construction Materials Research Laboratories at the University j.resconrec.2008.06.008.
Smuda, J., Dold, B., Spangenberg, J.E., Friese, K., Kobek, M.R., Bustos, C.A., Pfeifer, H.-
of Texas at Austin. Authors acknowledge the assistance provided
R., 2014. Element cycling during the transition from alkaline to acidic envi-
by the personnel working at these facilities and Prof. Maria ronment in an active porphyry copper tailings impoundment, Chuquicamata,
Juenger at the University of Texas at Austin in conducting this Chile. J. Geochem. Explor. 140, 23e40. https://doi.org/10.1016/
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study and the seed fund project supported by Corfo Engineering
Smuda, J., Dold, B., Spangenberg, J.E., Pfeifer, H.-R., 2008. Geochemistry and stable
2030 initiative.
436 F. Vargas, M. Lopez / Journal of Cleaner Production 182 (2018) 427e436