J. Am. Ceram. Soc.
, 88 [9] 23962401 (2005)
Journal
Phase Constitution During Sintering of Red Mud and Red MudFly Ash
Mixtures
Srinivasan Srikanthw,z, Ajay Kumar Ray, Amitava Bandopadhyay, and Bandari Ravikumar
Department of Materials, University of Leeds, Leeds LS2 9JT, UK
The phase constitution during the sintering of pure red mud and
red mudy ash mixtures was studied in the temperature range
of 900112501C. The phases formed at different sintering tem-
peratures were analyzed by X-ray powder diffraction. The phas-
es that are likely to form at equilibrium at any isotherm were
predicted using the Gibbs free energy minimization technique
and the databases provided in the FactSage software. Although
the thermodynamic prediction is in reasonable agreement with
the experimental results for the major phases, there is some dis-
agreement regarding the minor phases, especially the more com-
plex phases. The major limitation of the thermodynamic
approach presently is the non-availability of thermodynamic
data for several complex and multi-component solution phases.
I. Introduction
T HE solid residues generated during the high-pressure diges-
tion of bauxite with caustic soda in the Bayer process for the
production of alumina are known as red mud. For every ton of
alumina produced, almost 1.5 tons of red mud is generated in
the Bayer process.1 The disposal of red mud creates a major
problem because of its high NaOH content.2 Production of al-
uminum from alumina by the HallHeroult process is power
intensive and very often the major aluminum plants have a cap-
tive power plant. In the thermal power plants, y ash is gener-
ated as a major industrial waste.
In an attempt to utilize both these wastes together, an inves-
tigation was undertaken to develop a process for the manufac-
ture of building materials using a mixture of red mud and y
ash. Properties of the building materials such as abrasion resist-
ance, water absorption, cold crushing strength, exural strength,
stability, and corrosion resistance depend on the phase consti-
tution of the red mud, the sintering time and temperature and
the post-sintering phase constitution. The objective of the pre-
sent work is to study the changes in phase constitution during
sintering of red mud and red mudy ash mixtures at different
temperatures ranging from 9001 to 12501C.
II. Experimental Procedure
(1) Materials
Red mud samples were obtained from the ALCAN Chemicals
plant at Burntisland in Scotland, UK. The y ash samples were
J. E. Blendellcontributing editor
Manuscript No. 186585. Received October 30, 2002; approved July 25, 2003.
Supported by British Council, Calcutta under the Higher Education Link entitled
Recycling of Red Mud, Refractories and Flue Dust (Grant No. CAL/985/46).
w
Author to whom correspondence should be addressed. e-mail: srikanth_99@
yahoo.com
z y
Current address: National Metallurgical Laboratory Madras Centre, CSIR Madras
Complex, Post TTTI, Taramani, Chennai 600 113, India.
2396
DOI: 10.1111/j.1551-2916.2005.00471.x
r 2005 The American Ceramic Society
National Metallurgical Laboratory, Jamshedpur 831 007, India
Animesh Jha
collected from one of the thermal power plants of M/S Calcutta
Electric Supply Company, Calcutta, India. The chemical com-
positions on dry basis (dried at 1101C for 4 h) of the red mud
and y ash determined by X-ray uorescence and atomic ab-
sorption spectrophotometry are given in Table I.
(2) Characterization Studies
X-ray diffraction (XRD) analysis of pure red mud and the sin-
tered red mud1y ash samples were carried out with a dif-
fractometer using CoKa radiation (Ka 5 1.79026 A) (Siemens
D500, Germany).
(3) Sintering Studies
The red mud ground to a size of less than 150 mm (
100 mesh)
was mixed with 10, 20, and 30 wt% y ash, respectively, and was
compacted in a stainless steel die by a uni-axial hydraulic press
under a pressure of 50 MPa. The green pellets were dried in air
at room temperature for 48 h followed by drying in an air con-
vection oven. The oven was heated at a rate of 21C/min up to
1101C, at which it was held for 4 h. Sintering and isothermal
equilibration of the samples in a static air atmosphere was car-
ried out at various isotherms in the range 900112501C in a sil-
icon carbide furnace for periods ranging from 4 to 48 h. At low
temperatures, isothermal equilibration was carried out for 7
days. The furnace was heated to a pre-determined temperature
and was allowed to achieve temperature equilibration after
which the pressed samples of red mud and red mudy ash
mixtures were placed inside the hearth for sintering. After sin-
tering, they were removed from the furnace and allowed to
quench in air. The sintered samples were characterized by XRD.
(4) Equilibrium Thermodynamic Calculations
The various phases at equilibrium at any temperature was de-
duced from Gibbs free energy minimization technique incorpo-
rated in the FactSage software.y The equilibrium calculations
were carried out both with and without considering the solution
phases. The relevant solution phases for which thermodynamic
data is available in the FactSage software were carefully selected
based on the concentration range in which they successfully de-
scribe the thermodynamic properties. However, since the agree-
ment of experimental results with the thermodynamic prediction
did not show any improvement by including the formation of
solutions and since the thermodynamic properties of all the
multi-component solution phases are not well described, the
formation of solution phases were not considered in the subse-
quent calculations. All the invariant condensed phases for which
thermodynamic data are available in FactSage are automatically
incorporated in the free energy minimization calculations.
FactSage Programs and Databases, Version 5.1, THERMFACT Ltd., 447 Berwick,
Mount Royal, Quebec, Canada.
September 2005 Phase Constitution during Sintering of Red Mud and Red MudFly Ash Mixtures 2397

Table I. Chemical Composition (Dry Basis) of Red Mud and ries: (i) The phases that are originally present in bauxite and are
Fly Ash transferred to the red mud such as boehmite, diaspore, gibbsite,
hematite, goethite, lepidocrocite, limonite, rutile, anatase, pyrite,
Composition calcite, dolomite etc. and (ii) the phases formed during the alkali
Constituent (mass percent)
digestion i.e., sodium aluminum hydrosilicates, titanates of so-
Red Mud dium, calcium, or magnesium and calcined aluminum silicate.
Fe2O3 46 The phases detected by XRD at various sintering tempera-
Al2O3 20 tures for pure red mud and red mudy ash mixtures are given
TiO2 6 in Tables II and III in comparison with the equilibrium phases
SiO2 5 predicted at each temperature from the free energy minimization
calculations. A representative XRD pattern of the red mud
Na2O 8
sample sintered at 12001C for 48 h is shown in Fig. 2.
K2O 1
The XRD of the sintered samples of red mud and red mudy
CaO 1
ash mixtures (up to 20% y ash) indicates that the major phases
MgO 1 present are hematite (a-Fe2O3), NaAlSiO4, Fe2TiO5, and corun-
LOI 12 dum (a-Al2O3). The phase NaAlSiO4 exists as nepheline up to
Fly Ash 12001C and as carnegeite at 12501C. For the sintered red
Fe2O3 3.8 mud130% y ash mixture, mullite is present as the major phase
SiO2 59.9 instead of a-Al2O3 in the temperature range 900111001C and
Al2O3 29.2 TiO2 is present as Fe2Ti3O9 instead of Fe2TiO5 at lower tem-
TiO2 2.7 peratures (900111001C). As expected, the amounts of hematite
Alkaline oxides 0.3 phase decreases and the alumina- and silica-rich phase increases
Alkaline earth oxides 3.1 as the y ash content in the sample increases. In addition,
P2O5 1.4 some minor phases such as Na b-alumina, rutile (TiO2), Ca3-
Others 0.2 Fe2(SiO4)3, Mg4Al2Ti9O25, CaFeO2, Fe2Ti3O9 were detected by
XRD in some of the sintered samples. The phase composition
and transformation of red mud during sintering have been re-
ported in the literature.1,3,4 Yalcin and Sevinc3 reported only the
III. Results and Discussion
additional formation of sodium ferrite (NaFeO2) in comparison
The chemical analysis of red mud indicates predominantly the with the phases already present in red mud during the calcina-
presence of iron and aluminum and small amounts of titanium, tion of Turkish red mud at 5001C. Sglavo et al.4 have carried out
silicon, and sodium. The XRD pattern of the air-dried red mud is a detailed investigation on the thermal behavior of red mud, in-
shown in Fig. 1. It is seen from the XRD of air dried red mud cluding phase transformations on red mud sintered in air for 8 h
that iron is mostly present as goethite [a-FeOOH] and some in the interval 300114001C. Although they also observed the
as hematite, aluminum as Gibbsite [Al(OH)3], titanium as rutile formation of hematite, corundum, nepheline and NaAlSiO4 in
and sodium as sodium aluminum silicates or hydrosilicates. the red mud samples sintered between 9001 and 12001C, the
The characterization of the phases present in red mud derived formation of ferric pseudobrookite (Fe2TiO5), Ca3Fe2(SiO4)3,
from bauxites of various sources has been carried out by several and Mg4Al2Ti9O25 were not detected in their study. Instead,
workers.1,36 The phases detected in red mud fall in two catego- they found TiO2 to be present as rutile up to 11001C and as

Fig. 1. X-ray diffraction pattern of pure red mud.

 2398

Table II. Comparison of Thermodynamic Prediction with Experimental XRD Results for Pure Red Mud and Red Mud110% Fly Ash
Presence of the different phases in pure red mud and red mud10% y ash mixtures at different sintering temperatures

Pure red mud Red mud110% y ash

9001C 168 h 10001C 48 h 11001C 48 h 12001C 48 h 12501C 48 h 12001C 3 h 9001C 168 h 10001C 48 h 11001C 48 h 12001C 48 h 12501C 48 h 12001C 3 h

Phase Ex Th Ex Th Ex Th Ex Th Ex Th Ex Ex Th Ex Th Ex Th Ex Th Ex Th Ex

Hematite (a-Fe2O3)                      
Corundum (aAl2O3)       X X  X         X  X X
NaAlSiO4 X                     
Fe2TiO5  X  X  X  X              
Na b-alumina X  X X X X  X X X  X X X X X X X X X X X
Na8Ti5O14 X X X  X  X  X  X X X X X X X X X X X X
Na6(AlSiO4)@  X X X X X X X X X X X X X X X X X X X X X
6
Rutile, TiO2 X X X X X X  X  X X  X  X  X  X  X X
Na2Ti3O8 X  X  X  X  X X X X X X X X X X X X X X
CaAl2Si2O8 X X X X X X X X X X X X  X  X  X  X  X
Ca3Fe2(SiO4)#3  X  X  X  X  X   X  X X X X X X X 
Mg4Al2Ti9O@  X  X  X X X X X X  X  X  X X X X X X
25
CaFeO@ X X X X X X X X X X X  X  X  X  X  X X
2
Perovskite, CaTiO3 X  X  X  X  X  X X X X X X X X X X X X
Journal of the American Ceramic SocietySrikanth et al.

Spinel, MgAl2O4 X  X  X  X  X  X X  X  X  X  X  X
Al2Fe2O6 X X X X X X X  X  X X X X X X X X  X  X
Magnetite, Fe3O4 X X X X X X X  X  X X X X X X X X  X  X
, major phase; , minor phase; X, phase absent; @, thermodynamic data not available; #, not included for equilibrium calculations; Ex, experimental; Th, thermodynamic calculation.
Vol. 88, No. 9
 September 2005

Table III. Comparison of Thermodynamic Prediction with Experimental XRD Results for Red Mud with 20% and 30% y ash
Presence of the different phases in red mud 20% and 30% y ash mixtures at different sintering temperatures

Red mud120% y ash Red mud130% y ash

9001C 168 h 10001C 48 h 11001C 48 h 12001C 48 h 12501C 48 h 12001C 3 h 9001C 168 h 10001C 48 h 11001C 48 h 12001C 48 h 12501C 48 h 12001C 3 h

Ex Th Ex Th Ex Th Ex Th Ex Th Ex Ex Th Ex Th Ex Th Ex Th Ex Th Ex

Hematite (a-Fe2O3                      
Corundum (a-Al2O3)    X  X  X  X X X  X X X X  X  X 
NaAlSiO4         X             X
Fe2TiO5 X           X  X  X      
Fe2Ti3O9  X  X  X X X  X   X  X  X X X X X X
Rutile (TiO2)  X  X  X X X X X   X X X X X X X X X X
CaFeO@ X X  X X X X X X X X X X  X  X  X  X 
2
b-NaFe2O@ X X X X X X  X  X X X X X X X X X X X X X
3
NaAlSi3O8 X  X X X X X X X X X X    X  X  X  X
Mullite (Al6Si2O13) X X X  X  X  X X X  X     X  X X X
Al2Fe2O6 X X X X X X X  X  X X X X X X X X X X  X
CaAl2Si2O8 X  X  X  X  X  X X  X  X  X  X  X
Ca3Fe2(SiO4)3 X X X X X X X X X X X X X  X  X  X  X X
Cordierite (Mg2Al4Si5O18) X  X  X  X  X  X X  X  X  X  X  X
Na6Si8O19 X X X X X X X X  X X X X X X X X X X X X X
, major phase; , minor phase; X, phase absent; @, thermodynamic data not available; Ex, experimental; Th, thermodynamic calculation.
Phase Constitution during Sintering of Red Mud and Red MudFly Ash Mixtures
2399
2400 Journal of the American Ceramic SocietySrikanth et al.
Fig. 2. X-ray diffractogram of red mud sintered at 12001C for 48 h.
ulvospinel at higher temperatures. The CaO was mainly present
as Ca3Al2O6 in the sintered samples in their study. Their original
red mud samples (from Eurallumina, Porto Vesme, Italy) con-
tain much larger amounts of CaO compared with the red mud
used in the present study and further, the shorter sintering times
adopted in their study may not have been sufcient for the for-
mation of the more complex phases. No information is available
in the literature on the phase constitution of sintered red mud
and y ash mixtures.
The predicted equilibrium phase constitution from the free
energy minimization calculations is in very good agreement with
respect to the major phases a-Fe2O3 and NaAlSiO4 and in mod-
erate agreement for the corundum (a-Al2O3), mullite (Al6-
Si2O13), and ferric pseudobrookite (Fe2TiO5) phases. However,
the presence of minor phases such as rutile (TiO2), CaFeO2,
b-NaFe2O3, Ca3Fe2(SiO4)3, and Mg4Al2Ti9O25 observed exper-
imentally in some of the samples have not been predicted by
thermodynamic calculations. Additionally, some of the phases
such as Na8Ti5O14, perovskite (CaTiO3), spinel MgAl2O4, mag-
netite (Fe3O4), NaAlSi3O8, CaAl2Si2O8, Na2Ti3O8, and cordie-
rite (Mg2Al4Si5O18) predicted to form in small quantities (o5
wt%) at select compositions and temperatures are not observed
experimentally.
The disagreement between the experimentally observed phase
constitution and the thermodynamically predicted phases can be
attributed to several reasons: (i) the lack of thermodynamic data
in the literature for some of the observed phases, (ii) non-at-
tainment of the equilibrium phase constitution because of slow
diffusion rates in the time scale of the experiment, (iii) improper
description of thermodynamic properties of the multi-compo-
nent solution phases, and (iv) limitation of the detection of mi-
nor amount of phases by XRD. In the present case,
thermodynamic data for the phases CaFeO2, b-NaFe2O3, and
Vol. 88, No. 9
Mg4Al2Ti9O25 are not available in the FactSage database and
therefore their formation could not be predicted. It is possible
that the formation of complex phases such as Mg2Al4Si5O18,
CaAl2Si2O8, and NaAlSi3O8 that are theoretically predicted but
are not observed experimentally are constrained by slow kinet-
ics. The amounts of perovskite, spinel, and magnetite that are
predicted from thermodynamic calculations are found to be
lower than 5 wt% and is less likely to be detected by XRD. The
exact amount of these phases is dependent on the red mud to y
ash ratio and the sintering temperature.
IV. Conclusions
The change in phase constitution during the sintering of red
mud (ALCAN) and red mudy ash mixtures was studied be-
tween 9001 and 12501C by thermodynamic modeling and sinte-
ring experiments. The various phases present in the samples heat
treated at different isotherms were evaluated by XRD and pre-
dicted by thermodynamic modeling using free energy minimi-
zation technique. It is seen that the major phases formed during
sintering are predicted reasonably well by thermodynamic
modeling. The inability of thermodynamic modeling to predict
the formation of some of the observed phases is related to the
lack of thermodynamic data for these phases.
Acknowledgments
The authors thankfully acknowledge the kind support of Director, N. M. L. in
carrying out this investigation. The authors are thankful to the British Council,
Calcutta particularly to Dr. Ambar Ghose, Manager (Science, Technology and
Education), East India for the help and support in the link programme. The au-
thors also wish to thank ALCAN Chemicals, UK and CESC, Calcutta for pro-
viding the red mud and y ash samples, respectively.
September 2005 Phase Constitution during Sintering of Red Mud and Red MudFly Ash Mixtures 2401
4
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