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Journal of the European Ceramic Society 34 (2014) 20232033
a Geology Department, Faculty of Science, Ain Shams University, Cairo 11566, Egypt
Crystallography Department, Faculty of Science, Bremen University, Bremen 28359, Germany
c Paleontology Department, Faculty of Science, Bremen University, Bremen 28359, Germany
d Ceramic Department, National Research Centre, Dokki, Cairo 12622, Egypt
Received 16 November 2013; received in revised form 12 January 2014; accepted 17 January 2014
Available online 13 February 2014
Abstract
This work aims at studying rate of densification, resistance to hydration and slag attack of 0.02.0 wt.% ilmenite-doped MgO-dolomite refractories
fired at 14001700 C, in relation to their thermal equilibrium and microfabric. XRF, XRD, SEM, EDAX and mercury intrusion were used to
characterize the fired samples. The modular system MgO-MF(MA)-C2 S-M2 S was applied in determining their thermal equilibrium data. The rate
of hydration and attack by steel-slag were also measured using CLM.
It is concluded that doping the dolomitic-magnesite with 0.5 wt.% ilmenite leads to maximize rate of densification after firing for 4 h at only
1500 C. Direct-bonded MgO-MgO network is shown enclosing merwinite and monticellite with minor magnesio-ferrite spinel solid solution
ex-soluted within the periclase network. Due to the dense microfabric, the hydration resistance is enhanced 8 times compared with the un-doped
samples. Also, there is deeper infiltration of the slag/refractory reaction products of the un-doped MgO-dolomite sample as compared with the
doped one.
2014 Elsevier Ltd. All rights reserved.
Keywords: Dolomitic-magnesite; Densification; Microfabric; Hydration; Slag-attack
1. Introduction
Due to the shortage of natural magnesite (MgCO3 ) in Egypt,
other available MgO-rich raw materials, such as dolomiticmagnesite, dolomite and serpentine, were exploited and assessed
for the production of shaped and unshaped basic refractories.14
The Egyptian dolomitic-magnesite, occurs in Abu-Ramad area,
contains 515 wt.% CaO and up to 5 wt.% of other impurity
oxides (SiO2 , Al2 O3 and Fe2 O3 ).5 Therefore, it was assessed
for the production of shaped MgO-enriched dolomite refractories together with unshaped hot-repairing MgO-CaO mixes for
basic linings of the steel furnaces.6
Varieties of shaped and unshaped MgO-CaO basic refractories are worldwide produced from graded volume-stable grains,
processed by dead-burning their natural and synthetic material
batches up to 16001800 C.713 Dolomite and MgO-dolomite
refractories are produced by dead-burning dolomite (Ca, Mg
(CO3 )2 ) and/or dolomitic-magnesite raw materials. These are
classified according to free lime content into stable- and semistable types. In the stable types, all free lime reacts with SiO2 and
R2 O3 to form CaO-silicate and alumino-ferrite phases, respectively. These refractories are therefore characterized by higher
hydration-resistance and longer-storage life in comparison with
the semi-stable types, which have considerable amount of free
lime.713
Co-clinkered semi-stable MgO-enriched dolomite refractories are recently developed to have 6080 wt.% MgO with higher
bulk density, refractory quality as well as hydration and slagattack resistance than dolomite. This is mainly attributed to
growth of the magnesia crystallites with the formation of a solid
2024
A.M. Soltan et al. / Journal of the European Ceramic Society 34 (2014) 20232033
The major portions of the surface area exposed to humidity of the MgO-based refractories are the periclase crystallite
boundaries.3338 They suffer from hydration upon storage in
moist environments and form less refractory film layer of brucite
[Mg(OH)2 ] on the surface of the refractory. However, the intergranular silicate and alumino-ferrite phases showed less ability
to hydration than the periclase grains, and therefore can immune
MgO-dolomite refractories from the action of water vapor.3335
Post hydration, the volume of periclase usually shows 2.5fold expansion and the brucite easily dissociates when exposed
to high temperatures.39
This work mainly aims at optimizing the densification parameters of shaped Egyptian dolomitic magnesite powder sample,
doped with 0.02.0 wt.% fine Egyptian ilmenite powder, after
firing for 2 h at 14001600 C by means of linear shrinkage and
bulk density in relation to dopant content and firing temperature.
The dense doped and un-doped samples are selected to investigate their thermal equilibrium as well as extent of attack by
steel slag and hydration resistance, using pill test up to 1500 C
and steam-curing under atmospheric pressure, respectively. The
results of these investigations are discussed in the light of phase
composition and microfabric of the dense doped and un-doped
samples.
2. Materials and methods
2.1. Materials
The main material used is an Egyptian raw dolomiticmagnesite lump sample (50 kg), representing the available ore
exposed in Abu-Ramad area, South-East Eastern Desert. It was
received from the Egyptian Iron and Steel Company (EISCO).
In addition, a sample of 5 kg of the heavy ilmenite grain mineral,
separated from the Egyptian black sands, was delivered from ElNasr Mining Co. (NMC) to be used as minor additive or dopant
(02 wt.%). Each of the two samples was thoroughly mixed,
ground and then quartered to get separate raw representative
sample.
The raw materials were characterized for their mineral and
chemical composition using X-ray diffraction and fluorescence
(XRD and XRF) methods, as illustrated in Fig. 1 and Table 1,
respectively. Fig. 1 shows magnesite (Mg (CO3 )) (Card no. 360383) as a major mineral, beside lesser amounts of dolomite
(Ca,Mg(CO3 )2 ) (Card no. 36-0426), talc (3MgO4SiO2 H2 O)
(Card no. 29-1493), serpentine (3MgO2SiO2 2H2 O) (Card no.
02-0092) and quartz (SiO2 ) (Card no. 46-1045) minerals, in
descending order. On the other side, major ilmenite mineral
(FeTiO3 ) (Card no. 29-0733) is detected in the ilmenite sample with minor amount of hematite (Fe2 O3 ) (Card no. 33-0664).
The mineral composition of the raw materials is confirmed by
the XRF data of Table 1 which also outlines that the steel-slag
sample is mainly basic.
2.2. Methods
The raw magnesite and ilmenite materials were separately
ground to pass a 63 m sieve, then the fine magnesite powder
A.M. Soltan et al. / Journal of the European Ceramic Society 34 (2014) 20232033
2025
was intimately mixed (or doped) with 0.0, 0.5, 1.0 and 2.0 wt.%
of the fine ilmenite to prepare four batches. 500 g of each batch
was wet mixed for 1 h in an agate ball mill, dried overnight at
110 C and semi-dry pressed under a pressure of 50 MPa into
cylindrical rods of 25 mm diameter and 50 mm height. In
order to optimize the densification temperature, the shaped rods
were subsequently fired for 2 h at 1400, 1500, 1600 and 1700 C
in an electric muffle furnace, using a rate of 2 C/min for heating
and cooling. Selected samples were then fired for 1, 2 and 4 h at
14001600 C to study effect of soaking time on the densification parameters; namely, linear shrinkage and bulk density. The
latter parameter was related to the measured periclase density
(3.55 g/cm3 ).4 A Pascal Series mercury intrusion porosimeter
was also used for the determination of pore size distribution,
average porosity, pore diameter and surface area of the dense
samples.
Thermal equilibrium data, i.e. amounts of solid and liquid phases coexist in the fired samples were quantitatively
calculated in the solid state and at 1500 C assuming that equilibrium is attained. The calculations were based on the available
phase equilibrium data according to White and Richmond15 and
Solacolu.16
The fired bodies were also investigated for their solid-phase
composition by XRD and for detailed microfabric analyses
by SEM microscope, supplemented by EDAX, model (Quanta
Table 1
Chemical composition of the raw magnesite and ilmenite dopant as well as steel slag (wt.%, 0.5).
Sample
SiO2
TiO2
Al2 O3
Fe2 O3
MgO
MnO
CaO
P2 O5
Cr2 O3
L.O.I.
Magnesite
Ilmenite
Slag
4.9
3.2
8.0
0.0
40.5
0.1
0.0
1.2
0.7
0.9
51.7
30.0
34.6
0.5
2.0
0.0
1.5
11.0
6.0
0.5
47.0
0.5
0.1
1.1
0.0
0.3
0.0
52.7
0.0
0.0
2026
A.M. Soltan et al. / Journal of the European Ceramic Society 34 (2014) 20232033
Fig. 2. (a) Linear shrinkage of the un-doped and ilmenite-doped samples fired
for 2 h at (14001700 C); (b) linear shrinkage and (c) bulk density of the undoped and 0.5%-ilmenite doped samples fired at 14001600 C as a function of
soaking time (14).
A.M. Soltan et al. / Journal of the European Ceramic Society 34 (2014) 20232033
2027
Table 2
Calculated chemical and solid phase composition of the doped and un-doped MgO-dolomite dense grains with 1.3 CaO/SiO2 molar ratio.
Sample
Un-doped
Doped
MSi
SiO2
R2 O3
CaO
MgO
10.59
10.55
2.00
2.27
12.85
12.85
74.56
74.30
5.3
4.7
MCa
1.0
1.0
C3 MS2
CMS
[MF]s.s.
MgO
18.8
18.8
8.9
8.9
2.5
2.8
69.8
69.5
Fig. 3. XRD patterns of the un-doped and doped samples after firing for 4 h at 1500 C.
Table 3
Calculated thermal equilibrium data of the doped and un-doped MgO-dolomite grains at T2 = 1365
Sample
Un-doped
Doped
At 2
At T2 = 1365
and 1500 C.
At 1500 C (wt.%)
(wt.%)
MSi
MCa
C3 MS2
CMS
MgO
Liquid
MgO
Liquid
1.15
1.15
1.23
1.23
11.1
10.0
5.3
4.8
69.8
69.5
13.8
15.7
65.8
65.5
34.2
34.5
2028
A.M. Soltan et al. / Journal of the European Ceramic Society 34 (2014) 20232033
Table 4
Average micro-chemical analyses of the phases coexist in the doped and undoped samples after firing at 1500 C for 4 h.
Fig. 4. Modular system of the quaternary phase diagram: MgO-(MF-MA)-C2 SM2 S, given by Solacolu,16 for calculating thermal equilibrium data of magnesite
refractories on firing up to 1600 C.
the periclase by solution-precipitation and/or solid state mechanism results in dense and compact direct bonded MgO grains
in the doped sample when compared with the un-doped one
(Figs. 5 and 6).
Phases
Oxide
Un-doped (wt.%)
Doped (wt.%)
Periclase
MgO
Fe2 O3
99.10
0.90
98.70
1.30
MgO
SiO2
CaO
P2 O5
37.40
19.60
25.20
17.80
48.60
30.50
21.10
0.00
MgO
CaO
TiO2
Fe2 O3
Not-existed
61.70
16.20
20.10
1.70
Fig. 5. SEM-microfabric of the doped and un-doped samples after firing for 4 h at 1500 C. The doped sample is showing compact (a) directly bonded (b) (blue
arrows) periclase grains (point 1) with Ca-Mg silicate solid solution (point 2) and Ca-titanate (red arrow and point 3). The un-doped sample is showing less compact
(c), however directly bonded (d) periclase grains (point 1) with Ca-Mg silicate solid solution (point 2).
A.M. Soltan et al. / Journal of the European Ceramic Society 34 (2014) 20232033
2029
Fig. 7. Slag penetration depth and outside attacked horizontal surface area of
the un-doped and doped sample after firing for 1 h at 1500 C (a); Cathodoluminescent panoramic view of the vertically penetrated slag attacked areas in the
un-doped (b) and doped (c) samples after firing for 1 h at 1500 C.
2030
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Fig. 9. SEM-images showing slag attacked areas of the doped sample after firing
for 1 h at 1500 C; periclase (white arrow and point 1); Ca-Mg silicate solid
solution phases (red arrow and point 2) (a); Ca-titanate solid solution (point 3)
(a) and zoomed periclase grain crowded by ex-soluted magnesio-ferrite (white
arrows) (b).
Fig. 8. SEM-images showing slag attacked areas of the un-doped sample after
firing for 1 h at 1500 C. A white shield phase (black arrow and point 1) (a);
gray metallic iron particle (point 2) (a, b); periclase (white arrow and point 3)
(a); Ca-Mg silicate solid solution (red arrow and point 4) (a) and a zoom in the
attacked periclase grains crowded by ex-soluted magnesio-ferrite (white arrows)
(c).
metallic Fe-droplets together with white scattered spots of FeMn rich spinel are recorded (Fig. 8).28,29 Side by side with the
latter phases, the periclase and Ca-Mg silicate solid solution are
existed (Fig. 8). The attacked zone of the doped sample does not
show any new crystalline phases (Fig. 9).
The white phase of the un-doped sample is zoning the
periclase grains (Fig. 8a and b) and is enriched with Fe2 O3
(25.4 wt.%) and MnO (15.9 wt.%) (Table 5). The existence of
A.M. Soltan et al. / Journal of the European Ceramic Society 34 (2014) 20232033
2031
Table 5
Average micro-chemical analyses of the phases formed in the slag attacked zones of the un-doped and doped samples after attack for 1 h at 1500 C.
Phases
Oxide/element
Un-doped attacked
zone (wt.%)
Doped attacked
zone (wt.%)
3.10
8.40
44.00
1.90
0.80
25.40
15.90
Not-determined
MgO
SiO2
CaO
P2 O5
Al2 O3
Fe2 O3
MnO
14.04
5.00
15.53
45.29
23.14
Not-determined
O
Mg
Ca
Fe
Mn
Periclase
MgO
Fe2 O3
MnO
CaO
92.40
4.50
1.90
0.90
94.90
3.40
0.00
0.00
MgO
Fe2 O3
SiO2
CaO
P2 O5
Na2 O
MnO
1.10
2.00
19.30
68.40
8.20
0.10
1.10
9.60
1.40
27.90
55.10
5.90
0.00
0.00
Not-determined
MgO
SiO2
CaO
TiO2
Al2 O3
Fe2 O3
MnO
2.70
9.30
46.30
7.10
1.60
30.90
2.50
consequently smaller grain boundaries areas subjected to hydration. The periclase boundaries represent regions with higher
free energy which are more likely to react with water first,
then proceeds inside the grain.3638 The presence of ex-soluted
magnesio-ferrite on the cleavage planes of the il-doped sample
(Fig. 6a) is another reason for its higher hydration resistance
when compared with the un-doped sample.33
Fig. 10. Rate of hydration of the un-doped and doped samples after steam curing
up to 8 h.
2032
A.M. Soltan et al. / Journal of the European Ceramic Society 34 (2014) 20232033
4. Conclusions
1. Dense refractory MgO-dolomite grains with maximum bulk
density and relative density as well as minimum apparent
porosity, pore diameter and surface area are obtained after
doping the dolomitc-magnesite with 0.5 wt.% ilmenite and
firing for 4 h at only 1500 C.
2. Microfabric of the doped samples are composed of major
direct-bonded periclase-periclase network, enclosing Ca,
Mg-silicate-phases with minor magnesio-ferrite spinel solid
solution (MF-MA), ex-soluted within the periclase network.
3. Due to such dense microfabric, hydration resistance of the
doped samples is enhanced eight times, when compared with
the un-doped ones.
4. The slag/refractory interface of the doped samples also shows
higher resistance to attack by steel slag and exhibit minor
Ca-silicate-titanate solid solutions in direct contact with the
periclase crystallites.
5. The un-doped samples show shielding zones of Fe-Mn-rich
Ca-silicate solid solutions surrounding the MgO-crystallites,
leading to relatively deeper infiltration of the reaction products.
6. Periclase crystallites in both of the attacked samples are
characterized by extensive ex-soluted Fe-rich solid solutions
parallel to its cleavage planes.
Acknowledgements
This research work was fully funded by the GERSS-2011
program under the auspices of the DAAD foundation, Germany.
The authors express their deep gratitude to Prof. Dr. Reinhard
Fischer head of the Crystallography group and all group members at Bremen University, Germany, for saving most research
facilities used in this work. We are also very grateful to Dr. Jens
Wendler, Anne Hbner, Petra Witte and Ralf Btzel Geology Department, Bremen University for their sincere help and
hand-in-hand cooperation during implementation of the analyses.
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