Cement and Concrete Research 41 (2011) 847–853

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Cement and Concrete Research

j o u r n a l h o m e p a g e : h t t p : / / e e s. e l s ev i e r. c o m / C E M C O N / d e f a u l t . a s p

Structural investigation relating to the cementitious activity of bauxite

residue — Red mud
Xiaoming Liu a,⁎, Na Zhang b, Henghu Sun c, Jixiu Zhang b, Longtu Li b
a
Key Lab of Ecological and Recycle Metallurgy of Chinese Ministry of Education, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing,
Beijing 100083, China
b
State Key Lab of New Ceramics and Fine Processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
c
School of Engineering and Computer Science, University of the Pacific, Stockton, CA 95211, USA

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

Article history: The cementitious behavior of red mud derived from Bauxite-Calcination method was investigated in this
Received 7 August 2010 research. Red mud were calcined in the interval 400–900 °C to enhance their pozzolanic activity and then
Accepted 12 April 2011 characterized in depth through XRD, FTIR and 29Si MAS-NMR techniques with the aim to correlate phase
transitions and structural features with the cementitious activity. The cementitious activity of calcined red
Keywords:
mud was evaluated through testing the compressive strength of blended cement mortars. The results indicate
Thermal treatment (A)
X-ray diffraction (B)
that red mud calcined at 600 °C has good cementitious activity due to the formation of poorly-crystallized
Spectroscopy (B) Ca2SiO4. The poorly-crystallized Ca2SiO4 is a metastable phase which will transform into highly-crystallized
Ca2SiO4 (D) Ca2SiO4 with the increase of calcination temperature from 700 °C moving to 900 °C. It is the metastable phase
Red mud that mainly contributes to the good cementitious activity of red mud. This paper points out another promising
direction for the proper utilization of red mud.
© 2011 Elsevier Ltd. All rights reserved.

1. Introduction Recently, replacing clinker by pozzolanic materials and using new

alternative binders produced by industrial solid wastes have become a
Red mud is an alkaline leaching waste with pH typically 10–12.5. It prime interest in cement industry with attempts to lower CO2
is generated during Bayer process or Bauxite-Calcination method for emissions and decrease the production cost of cement. Some
alumina production. The disposal of red mud has caused serious materials with good pozzolanic properties such as fly ash and slag
environmental problems due to its high alkaline content (Na2O 2.0– can be utilized directly without heat treatment for the production of
6.0%). Red mud contains major oxides of CaO, SiO2, Fe2O3, Al2O3, TiO2 blended cement [4–7]. Whereas for other materials such as coal
and Na2O, and it can be used as an additive to cement, resulting in a gangue and red mud, their aluminosilicate minerals are expected to
good potential for the utilization of red mud in large quantities. The be partially destructed and become less crystalline at a relatively
chemical and mineralogical compositions of red muds all over the higher temperature, so that their pozzolanic properties could be
world are widely different depending on the sources of bauxite, the enhanced before being used for the preparation of blended cement
technological process (Bayer process or Bauxite-Calcination method) [8–10]. Zhang et al. [11] investigated the correlation between silicate
and storing ages. However, as a main constitute, iron oxide is polymerization and cementitious activity of coal gangue calcined at
generally occurring in red mud, and it is distributed in mineral phases different temperatures, and it has been found that phase transitions of
of hematite (Fe2O3) or/and goethite (FeOOH). These iron phases clay minerals caused the silicate polymerization degree of coal gangue
mainly control the color and settling properties of red muds [1]. to change with the increase of temperature, and coal gangue calcined
Goethite can be transformed into hematite during a high-temperature at 600 °C had good pozzolanic property due to the decomposition
calcination process, accompanying with the reinforcement of red products of clay materials to form active silica and alumina. Several
color and increase of settling rate [1]. As source of iron oxide, red mud papers [12–16] have been written on the characterization of red mud
has been investigated in the production of special iron rich cement through heat treatment. Sglavo et al. [12] carried out a detailed
clinkers [2], or been used as a pozzolanic pigment for colored concrete investigation on the thermal behavior of red mud, including phase
[3]. transformations of the red mud sintered in air for 8 h within the
interval 300–1400 °C. Srikanth et al. [13] studied the phase constitu-
tion during sintering of pure red mud and red mud–fly ash mixtures in
⁎ Corresponding author at: Room 810, Yejin Shengtai Building, University of Science
and Technology Beijing, Beijing 100083, China. Tel.: + 86 10 62332786; fax: + 86 10
the temperature range of 900–1250 °C. Jobbagy et al. [14] reported the
62333893. dependence of radon emanation of red mud and red mud–sawdust on
E-mail address: [email protected] (X. Liu). heat treatment in the temperature range of 100–1000 °C. Zhang and

0008-8846/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cemconres.2011.04.004
848 X. Liu et al. / Cement and Concrete Research 41 (2011) 847–853

Pan [15] made an investigation on the physicochemical characteristics Table 1

of red mud thermally treated at different temperatures (ambient, Chemical composition of dried red mud and clinker.

600–900 °C). However, most of the above reports on the character- Oxides (%) Red mud Clinker
ization of red mud have not investigated the dependence of
CaO 35.09 66.09
cementitious activity of red mud on heat treatment. Although Chen SiO2 18 21.94
et al. [16] simply investigated the properties of red mud heated at 450, Al2O3 6.31 5.27
600 and 800 °C and reported that the coordination of Al transformed Fe2O3 12.38 2.96
Na2O 2.71 0.3
from 4 to 6 in the red mud heated at 800 °C, the correlation between
K2O 0.45 0.7
structure change and cementitious activity of red mud calcined at MgO 1.13 0.88
different temperatures has not been figured out. TiO2 3.32 –
In the present work, the cementitious behavior of Bauxite- SO3 0.54 0.31
Calcination-method red mud calcined within the interval 400– LOI 20.07 0.67

900 °C has been investigated. The aim was to correlate solid-state

phase transitions and structural features deduced from TG–DTA, XRD,
FTIR and 29Si MAS-NMR techniques with the cementitious activity of crystalline, thermal analysis of the dried red mud was performed on a
red mud calcined at different temperatures. The cementitious activity Netzsch STA 449 C Thermal analyzer. TG–DTA analysis was performed
of calcined red mud was evaluated by means of testing the in the range of 80–1050 °C (stripping gas: dry N2 and heating rate:
compressive strength of blended cement mortars. This work provides 10 °C/min).
an important base for a long-term project on the utilization of red Powder batches (about 400 g red mud for each batch) were
mud in cement industry. calcined for lasting 3 h in a programmable electrical furnace at 400,
500, 600, 700, 800 and 900 °C. The calcined red mud samples were
2. Materials and experimental methods removed from the furnace and allowed to cool spontaneously to room
temperature in air.
2.1. Materials X-ray diffraction (XRD) analysis of the red mud samples at different
calcination temperatures were carried out with Rigaku D/max-RB X-ray
Red mud samples with age of 3 years old were obtained from diffractometer using CuKα radiation, voltage 40 kV, current 200 mA and
Shandong alumina refining plant, the process of which is Bauxite- 2θ scanning, ranging between 5° and 70°.
Calcination method. Ordinary Portland cement clinker from Beijing SEM observation was carried out on JSM-6460LV scanning electron
Xingang Cement Plant was used in this experiment, and its microscope for examination of micromorphological characteristics of
mineralogical phases are presented in Fig. 1. The chemical composi- red mud calcined at 600 °C.
tions of the red mud on dry basis (dried at 100 °C) and clinker Infrared spectra of the red mud treated at different temperatures
determined by X-ray fluorescence (XRF-1700) analyzer are given in were recorded on a Spectrum GX Perkin-Elmer Fourier transform
Table 1. infrared (FTIR) spectrometer using the KBr pellet technique.
29
Si solid-state magic-angle spinning (MAS) nuclear magnetic
2.2. Experimental procedure resonance (NMR) spectroscopy was carried out using a BRUKER-
AM300 spectrometer (Germany) operating at 59.62 MHz for the 29Si
The red mud was dried in an oven and ground down by using a ball resonance frequencies.
mill. The size distribution of the ground red mud particles obtained
from a laser diffraction particle size analyzer is shown in Fig. 2. It can 3. Results and discussion
be seen that the ground red mud particles are mostly within the range
of 3–70 μm with a mean of 23.2 μm. To decide an adequate calcination 3.1. TG–DTA analysis
temperature, at which the aluminosilicate materials composed in the
red mud are expected to be partially destructed and become less The TG–DTA diagram of dried red mud is given in Fig. 3. It shows
two major steps for the mass loss with the change in temperature. The
first step occurred in the range of 80–500 °C corresponding to the
2
1 physically absorbed water and chemically bound water. As the red
1. C3S
2. C2S 4.0
2 3. C3A
1 3.5
4. C AF
Volume Frequency (%)

4
3.0
1
2
1 2.5
1
2.0
4
1
3 1.5
1
1 1
2 2 1 1 1.0
2 1 1
0.5

0.0
0.1 1 10 100 1000
5 10 15 20 25 30 35 40 45 50 55 60 65 70 Particle Diameter (μm)
2θ / (° )
Fig. 2. Particle size distribution of red mud obtained from a laser diffraction particle size
Fig. 1. Mineralogical phases of clinker. analyzer.
 X. Liu et al. / Cement and Concrete Research 41 (2011) 847–853 849

TG /% DTA /(uV/mg)
Mass Change: -0.34 % exo
100
0.0
Mass Change: -8.60 %

95
-0.1
[1] RO.DSS
TG
DTA
90 -0.2

Mass Change: -12.67 %

85 -0.3
[1]

-0.4
80
[1]

100 200 300 400 500 600 700 800 900 1000
Temperature /°C

Fig. 3. TG–DTA diagram of dried red mud.

mud sample had been dried at 100 °C when it was used for patterns of the red mud uncalcined and calcined within the interval
thermogravimetric analysis, most of the physically absorbed water 400–900 °C are shown in Fig. 4. It can be seen that the major phases
dissipated in the drying process, and therefore the physically present in the uncalcined red mud are calcite (CaCO3), aragonite
absorbed water tested in the TGA diagram was about 0.34% of the (CaCO3), Ca2SiO4, perovskite (CaTiO3), hematite (Fe2O3), and gibbsite
total weight corresponding to the temperature range of 80–105 °C. (Al(OH)3). Perovskite and hematite are not affected by the heating
The temperature range of 105–500 °C with mass loss of 8.6% of the treatment up to 900 °C. Gibbsite cannot be detected in the sample
total weight was mainly related to the evaporation of chemically treated at 400 °C, neither crystalline Al2O3 is detected within the
bound water. The second step with significant mass loss of 12.67% of temperature interval 400–900 °C. According to the observation made
the total weight can be detected in the range of 500–750 °C, most by Sglavo et al. [12], it is thought that gibbsite (Al(OH)3 phase) here
likely to be corresponding to the release of CO2 during the considered decomposes to reactive aluminum oxide at 400 °C, the
decomposition of carbonates. It is notable that two endothermic crystallinity and stability of which are much lower than those of
peaks (around 600 °C and 725 °C) occurred within the interval 500– corundum (α-Al2O3). CaCO3 phases are present in aragonite and
750 °C, suggesting two carbonate phases present in the red mud calcite. It is noted that with the increase of temperature up to 600 °C,
sample. the peaks of aragonite diminish and they even completely collapse at
600 °C. Meanwhile, CaO can be detected in samples treated at 500 and
600 °C. This suggests the decomposition of aragonite to CaO in the
3.2. XRD analysis interval 500–600 °C. Calcite can be detected within the range of 400–
700 °C. However, it is observed that the peaks of calcite diminish
The elemental analysis and phase characterization of red mud obviously at 700 °C and eventually disappear at 800 °C, suggesting the
derived from bauxites have been investigated by several researchers decomposition of calcite into CaO in the interval 700–800 °C. These
[3,12,13,15–17]. However, red mud is a complex industrial waste, and results are consistent with the above TG–DTA analysis.
its chemical composition and mineralogical phases vary widely all Ca2SiO4 phase is present in the raw red mud used in this work. In
over the world. The chemical analysis of red mud used in this study alumina production by using Bauxite-Calcination method, bauxite
indicates predominantly the presence of calcium, silicon, iron and ores are generally mixed with sodium carbonate and limestone, and
aluminum, and small amounts of titanium and sodium. The XRD the mixtures are sintered under high temperature [17]. Due to most of
local bauxite ores in China contain a high portion of silicon, Ca2SiO4
can be formed in the calcination process (above 1200 °C) and
1.Perovskite-CaTiO3 5.Hematite-Fe2O3 6.Ca2SiO4 subsequently present in the bauxite calcination residue — red mud.
7
2.Calcite-CaCO3
5
7.Ca3Al2O6 8.CaO Ca2SiO4 constitutes the fundamental phase in the investigated
3.Gibbsite-Al(OH)3 1 9.Gehlenite-Ca2Al2SiO7 temperature interval 400–900 °C. It is interesting to notice that the
4.Aragonite-CaCO3 9 peaks of Ca2SiO4 increase gradually from 700 up to 900 °C, indicating
9 96 9
65 9 6 6 1 the formation of crystallized Ca2SiO4. Moreover, Ca3Al2O6 phase is
7 1
o
900 C 7 19 6 7 6 6 9 7 1
detected in specimen treated at 800 and 900 °C, and gehlenite
Intensity (cps)

6
6 61 7 1 (Ca2Al2SiO7) appears in the red mud calcined at 900 °C.
o
800 C 8 7 5
7 1 6 7
8
2
6 1 1
The main peaks of Ca2SiO4 in the red mud uncalcined and calcined
o
700 C 1 5 66 2 2
within the interval 400–900 °C are shown in Fig. 5 with an attempt to
6
1 obtain more detailed information about Ca2SiO4. The peaks of Ca2SiO4
600 C
o
1 8 52 2 6 2 2 2 1
are similar in the XRD patterns of red mud uncalcined and calcined at
6
o
500 C 1 484 52 2 6 2 4 12 4 21 400 and 500 °C. However, it is found that the peaks of Ca2SiO4 are very
o
1 44 52
6
2 6 2 4 12 4 21
obscure at 600 °C, suggesting poorly-crystallized Ca2SiO4 occurring in
400 C
6 1 the red mud calcined at 600 °C. Combining the SEM photograph of red
uncalcined 3 3 1 44 6 52 2 6 2 4 24 21 mud sample calcined at 600 °C (see Fig. 6), it is observed that the
particles of red mud at 600 °C were in poorly-crystallized or
5 10 15 20 25 30 35 40 45 50 55 60 65 70 amorphous forms. This indicates that the red mud calcined at 600 °C
2θ / (° ) may be more reactive than those calcined at other temperatures, and
may provide good cementitious property when used for blended
Fig. 4. XRD patterns of red mud uncalcined and calcined at different temperatures. cement.
850 X. Liu et al. / Cement and Concrete Research 41 (2011) 847–853

Ca2SiO4 900oC
o
800 C
848 519
999 919
700oC 975 923
845 519

o 712
900oC 600 C 1428
875 519
947
o o 713
800 C 500 C 1431 976 874
700oC
o 1476 858 713
400 C 991 875
600oC 1452

1471 858 713

500oC 994 874
uncalcined 1455
o 1480
400 C 713
858
1455 999 876
uncalcined
2000 1800 1600 1400 1200 1000 800 600 400

30 31 32 33 34 35 Wavenumbers (cm-1)
2θ / (° )
Fig. 7. FTIR spectra of red mud uncalcined and calcined at different temperatures.

Fig. 5. XRD patterns of Ca2SiO4 in the red mud uncalcined and calcined at different
temperatures.
[19,21,24] was detected. It is also noted that the intensity of this
observed band (519 cm− 1) increases with the calcination tempera-
3.3. FTIR analysis ture up to 900 °C, suggesting more and more Ca2SiO4 formed when
the red mud calcined from 700 to 900 °C. Meanwhile, the absorption
Fig. 7 displays infrared spectra of red mud uncalcined and calcined band at 947 cm− 1 (in the spectra of 700 °C) was split into two bands
within the interval 400–900 °C, respectively. The results concerning around 975 and 923 cm− 1 (in the spectra of 800 °C), and two sharper
main phases identified by FTIR analysis are summarized in Table 2. bands at 999 and 919 cm− 1 (in the spectra of 900 °C), indicative of the
Infrared spectra of the red mud uncalcined and calcined at 400 and formation of more highly crystallized Ca2SiO4 with the increase of
500 °C are rather similar, presenting analogous absorption bands. The temperature from 700 to 900 °C. In addition, two new bands at 845
bands around 1471–1480 cm− 1, and small shoulders at 858 cm− 1, and 848 cm− 1 appearing respectively in the IR spectra of red mud
respectively, are related to anti-symmetric C\O stretching (υ3) calcined at 800 and 900 °C can be related to symmetric Si\O
vibrations and out-of-plane C\O bending (υ2) vibrations in CO2− 3 stretching vibrations (υ1) in SiO4 tetrahedra of Ca2SiO4 [24],
ions of aragonite. However, these bands disappear in the infrared suggesting that the Ca2SiO4 formed in the red mud calcined at 800
spectra of red mud calcined at 600 °C and above 600 °C. This provides and 900 °C has highly symmetrical characteristic.
remarkably good correspondence with the XRD analysis, suggesting Combining the FTIR analysis with the results of TG–TDA and XRD,
the decomposition of aragonite between 500 and 600 °C. possible solid state reactions in the 400–900 °C interval can be
Infrared spectra of all samples with the exception of red mud deduced: (1) at 400 °C, the dehydration of gibbsite yielding reactive
calcined at 800 and 900 °C show bands around 1428–1455 cm− 1, Al2O3: 2Al(OH)3 → Al2O3 + 3H2O, (2) 500–600 °C, the decomposition
874–876 cm− 1 and 712–713 cm− 1, respectively, associated with of aragonite: CaCO3 → CaO + CO2, (3) at 600 °C, the formation of
anti-symmetric stretching (υ3), out-of-plane bending (υ2) and in- poorly-crystallized Ca2SiO4; (4) 700–800 °C, the decomposition of
plane bending (υ4) modes of CO2− 3 ions of calcite [18–21]. It is calcite: CaCO3 → CaO + CO2, (5) 700–900 °C, the formation of highly-
observed that these bands due to calcite decline with the increasing crystallized Ca2SiO4 with the increase of calcination temperature, (6)
temperature and they almost completely disappear when red mud 800–900 °C, the formation of Ca3Al2O6 from CaO and reactive Al2O3:
calcined at 800 °C, which confirms the XRD results and indicates that 3CaO + Al2O3 → Ca3Al2O6, and (7) at 900 °C, the formation of
most of calcite in red mud decomposes yielding CaO before 800 °C. gehlenite from CaO, reactive Al2O3 and reactive SiO2: 2CaO+ Al2O3 +
All spectra show bands in the range of 919–999 cm− 1 correspond- SiO2 → Ca2Al2SiO7.
ing to anti-symmetric Si\O stretching vibrations (υ3) in SiO4 Combining the TG data and chemical composition of red mud with
tetrahedra of Ca2SiO4 [18,19,21–24]. In IR spectra of red mud calcined the phases of Al(OH)3, CaCO3 and Ca2SiO4, more valuable information
at 700, 800 and 900 °C, a shoulder at 519 cm− 1 ascribed to out-of- can be obtained. Based on the CO2 loss (12.67%) recorded by TG, the
plane O\Si\O bending modes (υ4) in SiO4 tetrahedra of Ca2SiO4 amount of CaCO3 in the red mud was calculated to be 28.80%, and the
amount of CaO fixed in CaCO3 would be 16.13%. Considering that

Table 2
The main corresponding phases determined by FTIR for red mud uncalcined and
calcined at different temperatures.

Wavenumbers/cm− 1 Phases

Uncalcined 400 °C 500 °C 600 °C 700 °C 800 °C 900 °C

1480 1471 1476 – – – – Aragonite

1455 1455 1452 1431 1428 – – Calcite
999 994 991 976 947 975 999 Ca2SiO4
876 874 875 874 875 – – Calcite
858 858 858 – – – – Aragonite
3 µm 713 713 713 713 712 – – Calcite
– – – – 519 519 519 Ca2SiO4
– – – – – 845 848 Ca2SiO4
– – – – – 923 919 Ca2SiO4
Fig. 6. SEM photograph of red mud calcined at 600 °C.
 X. Liu et al. / Cement and Concrete Research 41 (2011) 847–853 851

35.09% CaO was contained in the red mud as seen in Table 1, the calcined at 900 °C has higher crystallized and symmetrical structure
amount of CaO not fixed as CaCO3 would be 18.96%. As shown in resulting in the decline of compressive strength.
Table 1, the content of Al2O3 in the red mud was 6.31%. If considering
that 6.31% of Al2O3 was fixed as Al(OH)3, the mass loss due to the
29
decomposition of Al(OH)3 would be 3.34%. However, the mass loss 3.5. Si MAS-NMR analysis
during 105–500 °C is 8.6% according to the TG analysis, which
29
suggests that there is another phase in the red mud losing water Si MAS-NMR appears as a powerful technique to probe structure
before 500 °C. Furthermore, it can be seen from Table 1 that the features of crystalline and poorly crystalline or amorphous phases. It
content of SiO2 in the original red mud sample was 18%, but Fig. 4 can distinguish the different SiQn structural units in aluminosilicates.
displays that the uncalcined red mud contain a small amount of In order to get an insight into the changes of structural units in red
Ca2SiO4, which indicates that an amorphous phase containing SiO2 mud during calcination, 29Si MAS-NMR was performed particularly on
could be occurring in the raw red mud. Liu et al. [17] reported there the uncalcined red mud, and samples at 600 and 900 °C.
were about 20% of amorphous materials in the red mud derived from Fig. 9 shows the 29Si MAS-NMR spectra for the red mud uncalcined
a combined Bayer process and Bauxite-Calcination method. Through and calcined at 600 and 900 °C, respectively. Two major environments
TEM observation, Zhang and Pan [15] also found that there were can be deduced from the 29Si NMR spectrum of uncalcined red mud.
certain amounts of amorphous aluminosilicates contained in the red One centered at −80 ppm is associated to SiQ1 unit (disilicates or
mud derived from Bauxite-Calcination method, the source of which chain end groups), and the other at −70 ppm is related to SiQ0 unit
was the same with the red mud we used in the present work. (orthosilicates). From the XRD pattern of uncalcined red mud (shown
Therefore, it is thought that amorphous aluminosilicates could be in Fig. 4), no aluminosilicate phases were detected except Ca2SiO4. It is
occurring in the red mud specimen used in this experiment, and these known that the SiQ0 unit is arising from Ca2SiO4 in the initial red mud.
amorphous aluminosilicates might decompose yielding reactive While for the left major content of SiQ1 unit, where is it from?
alumina and silica with the increase of calcination temperature, According to the discussion in the Section 3.3, certain amounts of
which would be involved in the formation of Ca2SiO4, Ca3Al2O6 and
Ca2Al2SiO7. -73

3.4. Evaluation of cementitious activity by compressive strength test

In order to find out an optimum calcination temperature under -88 -92

which the red mud would have good cementitious reactivity,
compressive strength of blended cement mortars at 3, 7 and 28 days
o
was tested according to Chinese Standard GB/T17671-1999 [25]. The 900 C
blended cement was composed of 50% red mud, 45% clinker and 5%
gypsum. Fig. 8 displays the compressive strength results as a function
of calcination temperature. The compressive strength values (at 3, 7
-68
and 28 days) of blended cement mortars changed with the calcination
temperature. It can be safely stated that calcination temperature has a
significant effect on the cementitious behavior of red mud. According
to the test results, the best 28-day compressive strength value of
34.15 MPa was obtained by blended cement produced with red mud
calcined at 600 °C. This confirms the result of XRD analysis that red
mud calcined at 600 °C has good cementitious activity due to the o
600 C
-82
formation of poorly-crystallized Ca2SiO4. Although the amounts of
Ca2SiO4 and Ca3Al2O6 occurring in the red mud calcined at 900 °C
were higher than those present in the red mud calcined at 800 °C, the
compressive strength values (at 3, 7 and 28 days) of red mud calcined
at 900 °C were slightly lower than those at 800 °C. This can be
explained from two viewpoints: (1) the formation of gehlenite
-80
(Ca2Al2SiO7) has an unfavorable effect on the cementitious behavior
of red mud calcined at 900 °C, and (2) Ca2SiO4 formed in the red mud

35
Compressive strength (MPa)

3d
30 7d
-70
25 28d

20 uncalcined

15
10
5
0
uncalcined 400 500 600 700 800 900
Temperature (oC) 50 0 -50 -100 -150
Chemical shift / ppm
Fig. 8. Compressive strength of red mud blended cement mortars versus calcination
29
temperature. Fig. 9. Si MAS-NMR spectra of red mud uncalcined and calcined at 600 and 900 °C.
852 X. Liu et al. / Cement and Concrete Research 41 (2011) 847–853

amorphous aluminosilicates were thought to be contained in the red −88 ppm, suggesting that gehlenite formed in the red mud calcined
mud derived from Bauxite-Calcination method. Amorphous phase is at 900 °C has structural units of SiQ3 and SiQ3(1Al). It is this highly
generally hard to be detected by XRD technique, but it can be figured polymerized structure arising from Ca2Al2SiO7 observed in the
out through MAS-NMR analysis. The 29Si MAS-NMR spectrum for the present study that plays unfavorable effect on the cementitious
uncalcined red mud proves that, except with small amount of Ca2SiO4, activity of red mud calcined at 900 °C.
most of the siliceous materials are presented as SiQ1 unit arising from Comparison among 29Si MAS-NMR spectra of uncalcined red mud
amorphous aluminosilicates. and red mud calcined at 600 and 900 °C shows that the red mud
29
Si NMR spectrum of red mud calcined at 600 °C shows significant calcined at 600 °C is mainly composed of SiQ0 unit corresponding to
differences from that of uncalcined red mud. It displays a major peak poorly-crystallized Ca2SiO4. Combining the results of XRD and FTIR
at − 68 ppm originating from SiQ0 unit and a negligibly smaller one at analysis, it is concluded that the poorly-crystallized Ca2SiO4 present in
−82 ppm related to SiQ1 unit. Compared to the uncalcined red mud, the red mud at 600 °C is a new formed phase by reaction 2CaO +
the general characteristic of the spectrum for the red mud calcined at SiO2 → Ca2SiO4, in which the reactive SiO2 is derived from the
600 °C is a significant increase of SiQ0 unit accompanying with a decomposition of amorphous aluminosilicates. The poorly-crystal-
decrease of SiQ1 unit, which reflects that SiQ1 unit transforms to SiQ0 lized Ca2SiO4 is a metastable phase which will transform into highly-
unit with the increase of calcination temperature up to 600 °C. It crystallized Ca2SiO4 with the increase of calcination temperature from
indicates that most of the siliceous materials are presented as SiQ0 700 moving to 900 °C. It is the metastable phase that mainly
unit in the red mud calcined at 600 °C. From this point of view, it is contributes to the good cementitious activity of red mud at 600 °C.
believed that large amounts of poorly-crystallized Ca2SiO4 have been
formed at 600 °C resulting from the decomposition of amorphous
aluminosilicates. 4. Conclusions
29
Si NMR spectrum of red mud calcined at 900 °C is very different
from both of the above spectra. It shows a major content of SiQ0 unit in An in-depth characterization of red mud has been performed to
connection with a sharper peak centered at − 73 ppm, indicative of investigate the phase transitions and structural features in relation to
the highly-crystallized Ca2SiO4. In addition, it displays two bands at cementitious activity during calcination within the interval 400–
−92 and − 88 ppm assigned to SiQ3 and SiQ3(1Al) units, respectively. 900 °C. This study provides an incisive understanding for the
According to the XRD pattern of red mud calcined at 900 °C (shown in cementitious behavior of red mud derived from Bauxite-Calcination
Fig. 4), Si is presented in phases of Ca2SiO4 and Ca2Al2SiO7 (gehlenite). method.
It is obvious that Ca2SiO4 has the orthosilicate structure of SiQ0 unit, so The major phases present in the raw red mud are calcite (CaCO3),
is it possible that the observed SiQ3 and SiQ3(1Al) units correspond to aragonite (CaCO3), Ca2SiO4, perovskite (CaTiO3), hematite (Fe2O3),
gehlenite? In the literature [26], it is reported that akermanite and gibbsite (Al(OH)3). Perovskite and hematite are not affected by
(Ca2MgSi2O7) has a 29Si NMR chemical shift at −73.9 ppm related to the heat treatment up to 900 °C. The solid state reactions in the
SiQ1 unit. However, there is little information reported for the 29Si interval 400–900 °C can be deduced: (1) at 400 °C, the dehydration of
NMR chemical shifts of Ca2Al2SiO7. Gehlenite is a single layer silicate, gibbsite yielding reactive Al2O3, (2) 500–600 °C, the decomposition of
and its structure [27] is shown in Fig. 10. In each unit cell, the two aragonite, (3) at 600 °C, the formation of poorly-crystallized Ca2SiO4,
tetrahedrally coordinated T1 sites are always occupied by Al atoms, (4) 700–800 °C, the decomposition of calcite, (5) 700–900 °C, the
whereas the four tetrahedral T2 sites are disordered, with equal formation of highly-crystallized Ca2SiO4, (6) 800–900 °C, the forma-
numbers of Al and Si atoms distributed on them [28]. As shown in tion of Ca3Al2O6, and (7) at 900 °C, the formation of gehlenite
Fig. 10, the T2 sites are grouped into pairs. There is no nearest (Ca2Al2SiO7).
neighboring T2\O\T2 linkage between pairs, but T2\O\T2 pairs are Calcination temperature has a significant effect on the cementi-
connected through the linkage of T1 sites to form a single layer tious activity of red mud due to the phase transitions during the
structure. Each T2 tetrahedron has three bridging oxygen and an calcination process. It is found that red mud calcined at 600 °C in this
apical oxygen. Due to the T2 sites that are disordered, T2\O\T2 pairs study had the best cementitious activity due to the formation of
could be in forms of Si\O\Al or Si\O\Si. Thus, it is thought that poorly-crystallized Ca2SiO4. With the increase of calcination temper-
structural unit of SiQ3 occurs when T2\O\T2 pairs presenting as ature from 700 to 900 °C, more and more Ca2SiO4 formed in the
Si\O\Si form, and SiQ3(1Al) unit appears when T2\O\T2 pairs calcined red mud samples, and the crystallinity of Ca2SiO4 also
presenting as Si\O\Al form. This interpretation is perfectly consis- increased.
tent with the above 29Si NMR analysis for the bands at −92 and 29
Si MAS-NMR spectroscopy has shown progressive structural
changes from the red mud uncalcined to the red mud calcined at
900 °C: SiQ1 and SiQ0 units (uncalcined sample) to major content of
SiQ0 unit (sample at 600 °C) and finally to SiQ0, SiQ3 and SiQ3(1Al)
units (sample at 900 °C). Combining the results of XRD, FTIR and 29Si
MAS-NMR analysis, it is concluded that the poorly-crystallized
Ca2SiO4 present in the red mud at 600 °C is a new formed phase by
reaction 2CaO + SiO2 → Ca2SiO4, in which the reactive SiO2 is derived
from the decomposition of amorphous aluminosilicates. The poorly-
crystallized Ca2SiO4 is a metastable phase which will transform into
highly-crystallized Ca2SiO4 with the increase of calcination temper-
ature from 700 moving to 900 °C. It is the metastable phase that
mainly contributes to the good cementitious activity of red mud at
600 °C.
This study provides a fundamental point for the use of red mud as
clinker replacement for the production of blended cement, which
points out another promising direction for the proper utilization of
red mud in large quantities. It is economically viable to perform a
Fig. 10. The unit cell of gehlenite (Ca2Al2SiO7) structure [24]. 1 and 2 marked represent 600 °C calcination of red mud to improve its cementitious properties,
T1 and T2 tetrahedra, which are two distinct tetrahedral sites. and using the subsequent red mud to develop blended cement not
 X. Liu et al. / Cement and Concrete Research 41 (2011) 847–853 853

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