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Journal of the European Ceramic Society 34 (2014) 20232033

Densification and resistance to hydration and slag attack of ilmenite-doped


MgO-dolomite refractories in relation to their thermal equilibrium and
microfabric
Abdel Monem Soltan a, , Michael Wendschuh b , Helmut Willims c , Mohamed Serry d
b

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

Corresponding author. Tel.: +20 1064758849.


E-mail addresses: abdelmonemsoltan2013@gmail.com,
abdelmonemsoltan@gmail.com (A.M. Soltan).
0955-2219/$ see front matter 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jeurceramsoc.2014.01.030

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

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and direct-bonded MgO-network. This network encapsulates the


free lime and low-melting calcium-silicate and alumino-ferrite
phases in its interstitial spaces.714
Solid phase composition of the MgO-CaO refractories could
be revealed by studying the solid-phase relationships within the
quaternary composition diagram: MgO-CaO-Fe2 O3 (Al2 O3 )SiO2 as given by White and Richmond.15 Assuming that
equilibrium is attained on firing the MgO-CaO grains up to
1600 C, the diagram shows different phase assemblages
which would occur in the fired grains. The type and amount
of these phases are affected by the CaO/SiO2 (C/S) molar ratio
that ranges between >3 and <1.15
The thermal equilibrium of the MgO-CaO grains with a C/S
molar ratio between 2.0 and <1.0 could be studied by using a
modular system of the phase diagram: MgO-C2 S-M2 S-MFs.s.,
as given by Solacolu.16 Meanwhile, thermal equilibrium of
grains with a C/S molar ratio of >3.0 can be investigated using the
modular system of the quaternary phase diagram: CaO-MgOC2 S-C4 AF, given by Serry and Barbulescu.17 These data play the
decisive role in controlling phase composition, microstructure
and properties of these refractories.717
The rate of sintering as well as properties of the MgOCaO refractories could be improved by adding limited amounts
of certain oxide mineralizers or dopants, e.g. Fe2 O3 , TiO2
and ilmenite (FeTiO3 ). Type, amount and cationic size of
these additives control the grain growth and phase distribution or microfabric of these refractories.18,19 The increase
in crystallite size or grain growth of magnesia usually leads
to decrease in its surface area and interstitial open pores,
which makes the crystals directly-bonded and less reactive for
slag infiltration.20,21 The high degree of sintering is reflected
from the high amount of solidsolid necks formed by an
incipient solutionreprecipitation and/or solid state sintering
mechanisms.21,22
The corrosion resistance of the magnesia-based refractories increases by addition of 1 wt.% Fe2 O3 due to the high
diffusion of ferric oxide into the periclase crystals forming
magnesio-ferrite spinel (MgOFe2 O3 ), which results in developed direct-bonded periclase crystals.23 The low Fe2 O3 content,
high CaO/SiO2 ratio as well as increased sintering temperature,
longest dwell time and lowest cooling rate are the major parameters enhancing grain growth of the periclase.24,25 Generally,
the main factors affect capability of refractories to withstand
the action of slag attack under service conditions are the reactivity of slag as well as phase composition and microfabric of
refractories.714 In the MgO-based refractories, the interstitial
CaO- and/or MgO-silicate and alumino-ferrite phases binding
the periclase crystallites are the weakest microstructural areas
to resist slag attack.26,27
The corrosion rate is much severe in case of FeO-rich slags,
where iron metal particles (<10 m) could be formed28 as well
as deeply infiltrated FeO is reduced to its metal state at the
slag/refractory boundary.29 The periclase grains in contact with
the slag at the refractory hot face also undergoes an increase
of the FeO content changing the MgO grains into a magnesiowustite (Mg,Fe)O solid solution as dendrites on the periclase
cleavage planes.3032

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

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Fig. 1. XRD patterns of the raw magnesite and ilmenite materials.

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

FEG 250), with accelerating voltage of 200 V to 30 kV and


magnification of 610 up to 6,400,000. Before microstructure
investigations, the samples were polished using different polishing plates with ethanol, ultrasonic cleaned and thermally etched
for 1 h at 1300 C.
SEM images were used for investigating the detailed samples microfabric as well as for analyses of the mean crystal-size
of the coexisting phases by using a standard line mean intercept method.40 The median crystal size was determined from
intercept measurements applying: D = 1.56L, where (D) is the
average crystal size and (L) is the average intercept length. It was
done by an automatic image analysis using Image J free software for 46 images, where 7001050 crystals were analyzed
in average for each sample.
The dense samples were also tested for their hydration and
slag attack resistance. The samples were subjected to water vapor
in a humidity chamber with a 92% relative humidity at ambient
temperature of 25 C up to 8 h under atmospheric pressure. Then,
the increase in weight due to hydration was calculated. The pill
test was conducted to assess slag attack resistance, after pressing 2 g steel-slag powder into cylindrical pellets with 10 mm
diameter, centered on the surface of the test samples and all were
fired for 1 h at 1300, 1400 and 1500 C. After slicing the fired
slag/refractory samples into two halves, the depth of slag infiltration was measured at the polished interface surfaces using the

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

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cold cathode luminescence (CCL) microscopy. This was done by


using a Technosyn8200MK11 cold cathode luminescence stage
mounted on an Olympus BH-2 microscope with a beam current
of 250 A and voltage of 15 kV as well as an Olympus DP72
digital camera for imaging. For cathode luminescence examination, the samples were stacked on a glass slide using Araldite, left
under vacuum for 24 h, sawed and then re-polished using ethanol
before examination. On the other hand, detailed microfabric of
the attacked areas was investigated by the SEM supplemented
by EDAX.
3. Results and discussion
Linear shrinkage data of the doped and un-doped MgOdolomite samples are shown in Fig. 2a as a function of firing
temperature (14001700 C) at 2 h soaking time. At 1400 C,
linear shrinkage is gradually increased from 28.7 to 30.8% by
increasing ilmenite content from 0.0 to 2.0 wt.%, respectively.
On rising firing temperature to 1500 C, all samples generally
show an abrupt increase in linear shrinkage from 2831 to
3436%. Further rising of firing temperature of the doped samples up to 16001700 C leads to similar slight increase in linear
shrinkage, without significant differences, up to 3536%, while
the un-doped one shows parallel decrease to 34%. Accordingly, sample doped with 0.5 wt.% ilmenite was selected to study
effect of soaking time (14 h) at 1500 C, on its densification
parameters by means of linear shrinkage and bulk density as
compared with the un-doped one (Fig. 2b and c).
It is evident that rising soaking time from 1 to 4 h leads to
gradual increase in the densification of both the doped and undoped samples. However, the doped sample shows relatively
higher values of linear shrinkage and bulk density than the undoped one at all soaking times up to 4 h. Maxima of linear
shrinkage (36.5%) and bulk density (3.34 g/cm3 , i.e. 94% relative density) occur in the doped sample as compared with the
corresponding of the un-doped one (35.6%, 3.27 g/cm3 and 92%,
respectively). This is mainly attributed to doping with 0.5 wt.%
ilmenite (FeTiO3 ), which enhances formation of Fe- and Tirich liquid phase as well as surface and bulk diffusion of Mg2+
ions, leading to growth and direct-bonding of the MgO-MgO
network.1822
The results of densification could not be interpreted in the
light of gross mineralogy, where both of the doped and un-doped
samples have more or less the same solid phase composition
according to their chemical composition as well as modulei
of silica (MSi ) and calcia (MCa ) as summarized in Table 2.
Both grains have 1.3 CaO/SiO2 molar ratio and must contain,
after firing for 4 h at 1500 C, major free periclase (69 wt.%
MgO) with lesser amounts of merwinite (1819 wt.% C3 MS2 )
and monicellite (89 wt.% CMS) silicate phases as calculated
according to White and Richmond.15 In addition, minor amount
(2.52.8 wt.%) of a magnesio-ferrite (MgFe2 O4 ) spinel solid
solution should coexist with the latter phases and accommodate
other R2 O3 impurities, e.g. Al2 O3 , MnO and Cr2 O3 in its octahedral sites as calculated in Table 2. The major periclase (Card
no. 71-1176) and Ca, Mg-silicate phases, monticellite (Card no.
84-1322) and merwinite (Card no. 02-0949), are detected by

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).

XRD in Fig. 3, while the minor MgFe2 O4 spinel solid solution


could not due to its small amount and/or dissolution in the major
periclase phase.
When the chemical composition of the doped and un-doped
samples is plotted on the modulus system of the quaternary diagram: MgO-M2 S-C2 S-(MF-MA) of Solacolu,16 by means of
modulei of silica (MSi ) and calcia (MCa ), their compositions exist
within the subsystem: MgO-C3 MS2 -CMS-(MF-MA) as shown
in Fig. 4. The quaternary eutectic point (T2 ) of this subsystem
exists at 1365 C, at which spinel s.s. phase would be completely dissolved with some of the silicate phases to form 13 to
16 wt.% liquid phase, which coexist with 6970 wt.% free periclase (MgO) in the doped and un-doped samples (Table 3). On
firing between 1400 and 1500 C, complete dissolution of the

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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

Chemical composition (wt.%)

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

Solid phase composition (wt.%)

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.

silicate phases gradually occurs together with up to 4 wt.% of


periclase. This results in development of the liquid phase level,
up to 3435 wt.% at 1500 C, which coexist with 6566 wt.%
periclase (Table 3). This can interpret the relatively higher rate
of densification of both the doped and un-doped samples on
rising firing temperature from 1400 to 1500 C. However, the
relatively higher densification of the 0.5-il doped samples than
the un-doped ones at 1500 C could be related to effect of the
minor Fe and Ti ions of ilmenite in enhancing densification of
the doped grains in the solid state and also by liquid phase.
The SEM-microfabric of the doped and un-doped samples
fired for 4 h at 1500 C is exhibited in Fig. 5ac. The doped sample shows relatively higher degree of solid MgO-MgO direct
bonding, which encloses most of the Ca, Mg-silicate phases
within its interstitial spaces as compared with the un-doped
one (Fig. 5c and d). In the doped sample, iron ions are mostly

diffused into periclase forming magnesio-ferrite spinel s.s. phase


(MgFe2 O4 ), which ex-soluted on its cleavage planes (Fig. 6a)
causing higher degree of densification.41 Meanwhile, the Ti
ions have limited affinity to diffuse into the periclase grains
by vacancy formation mechanism due to the difference in the
cations radii.23,42,43 Therefore, the latter ions are concentrated in
the developed liquid phase increasing its flux affinity to promote
Mg+2 transport and periclase grain growth.18 This is achieved
by dissolution of some periclase, diffusion of the Mg+2 through
the Ti rich liquid and final deposition of MgO epitaxial layers
on the growing periclase seeds (Fig. 6b).
As well, the formed liquid could be differentially crystallized,
resulting in a synthetic corona structure in which the MgO crystallizes first followed by the Ca-silicate rich phases (Fig. 6c). The
solid state sintering is also evidenced in the doped sample by the
high degree of solid-solid necks (Figs. 5 and 6). The growth of

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

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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

Ca-Mg silicate s.s.

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

Ca-Mg titanate s.s.

61.70
16.20
20.10
1.70

Rather than microfabric, micro-chemistry of the mineral


phases confirms that periclase and Ca-Mg-silicate solid solutions are the main mineral phases in both samples together
with minor Ca-Mg-titanate solid solutions in the doped sample
(Fig. 5b, d and Table 4). In the un-doped sample, periclase has
relatively higher MgO (99.1 wt.%) and lower Fe2 O3 (0.9 wt.%)
as compared with the doped one (98.7 and 1.3 wt.%, respectively) (Table 4). In both samples the presence of Ca-Mg-silicate
solid solution is confirmed as a major phase among the direct
bonded periclase network (Fig. 5b and d). In addition, minor
bright particles of Ca-Mg titanate solid solution phase is also
detected in the doped sample (Fig. 5b).

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).

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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.

Fig. 6. SEM-microfabric of the doped sample after firing for 4 h at 1500 C;


(a) arrangement of ex-soluted magnesio-ferrite on the cleavage of the periclase
grains; (b) the solid-solid necks (blue arrows) and the crescent-like MgO overgrown epitaxial layer (bracketed between white dashed lines) on a periclase
grain as a seed (red arrow) and (c) the synthetic corona zoning texture of the
periclase (black arrow), Ca-Mg silicate solid solution (bracketed between white
dashed lines) and the brighter Ca-silicate phase in the core (white arrow).

The median crystal size of the periclase and Ca-Mg silicate


and titanate solid solution phases (7.7 and 2.9 m) in the doped
sample are smaller as compared with the un-doped one (13.0 and
4.3 m). This is attributed to the higher degree of periclase direct
bonding occurred in the former sample which limited the available spaces to precipitate the Ca-Mg silicate and titanate solid
solutions on cooling. This may be another reason for enhancing
densification of the doped sample.

The behavior of the doped sample against slag attack at


13001500 C is compared with the un-doped one in terms of
attacked surface area and penetration depth as shown in Fig. 7a.
It is shown that both samples have lower rates of attack by slag
penetration and surface area at 1300 and 1400 C. However, the
rate of attack is increased at 1500 C with lower slag penetration
and higher surface area in the doped sample as compared with
the un-doped one (Fig. 7a). The penetration depth calculated
from the cathode-luminescence image (Fig. 7b and c) shows
that the mean penetration depth within the un-doped sample
(1 mm) (Fig. 7b) is relatively higher than the doped (0.6 mm)
(Fig. 7c) sample. This is mainly attributed to the relatively higher
degree of direct bonding among the periclase grains in addition
to the lower porosity (2.02%) as well as average pore diameter
(0.01 m) of the latter sample.
The slag attack imposed the generation of new crystalline
phases only in the attacked zone of the un-doped sample. A
white shield of a Fe-Mn rich Ca-silicate solid solution, gray

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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

this phase as a shielding zone surrounding the periclase grains


may be due to its early crystallization from a silicate rich melt differentially crystallized to result in a late Ca-silicate solid solution
low in Fe2 O3 and MnO (2.0, 1.1 wt.%, respectively) (Fig. 8a)
(Table 5). Along the boundary between the attacked and nonattacked zone, the un-doped sample is showing gray metallic
Fe-droplets partially coating the periclase (Fig. 8b). The latter phase resulted from the reduction of the deeply infiltrated
FeO-slag and is mainly composed of Fe (45.3 wt.%) and Mn
(23.1 wt.%) (Table 5).28,29
The attacked periclase grains in both the un-doped and
doped samples (Figs. 8b and 9b) are characterized by extensive
ex-soluted phases parallel to the periclase cleavage planes. However, the periclase in the un-doped sample is more crowdie by
this ex-soluted phase which is branched wherever the cleavage
planes are intersecting giving dendritic crystals (Fig. 8c).30 As
well, they are distributed along the intra-crystal boundaries proving their ex-solution origin (Fig. 8c). This periclase is of higher
Fe2 O3 (4.5 wt.%) and MnO (1.9 wt.%) contents when compared
with that of the doped sample (3.4 wt.% Fe2 O3 and depleted
MnO) (Table 5). This could be due to the relatively higher

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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

Fe-Mn-rich Ca-silicate white shields

MgO
SiO2
CaO
P2 O5
Al2 O3
Fe2 O3
MnO

14.04
5.00
15.53
45.29
23.14

Not-determined

Fe-rich gray metallic shield

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

Ca-Mg silicate s.s.

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

Fe-rich Ca-titanate s.s.

MgO
SiO2
CaO
TiO2
Al2 O3
Fe2 O3
MnO

2.70
9.30
46.30
7.10
1.60
30.90
2.50

diffusion of slag to the periclase grain edges in the un-doped


sample causing their brighter appearance in places (Fig. 8c).28
The Ca-silicate solid solution phase exists among the periclase grains in both samples. It is directly contacted with the
periclase grains in the doped sample (Fig. 9a), however zoned
with the white shield phase in the un-doped sample (Fig. 8a and
b) keeping it away from the direct contact with the periclase
grains. This Ca-silicate solid solution is enriched with CaO and
Fe2 O3 with a major decrease in MgO compared with its composition before attack in both samples (Tables 4 and 5). The minor
Fe-rich Ca-titanate phase (Fe2 O3 30.9 wt.%) (Fig. 9a) is only
characterizing the doped sample. It is enriched with CaO and
MnO from the slag with a marked decrease in MgO and TiO2 as
compared with the un-attacked composition (Tables 4 and 5).
Fig. 10 shows that the doped sample is more resistant to
hydration when compared with the un-doped sample. The hydration resistance of the doped sample is enhanced about 8 times
than that of the un-doped after 8 h steam curing. This could
be interpreted in terms of the denser microfabric of the ildoped sample which gives lower porosity (2.02%) as well as
average pore diameter (0.01 m) and consequently low surface
area (0.90 m2 /g) as revealed from the mercury intrusion analysis. The il-doped sample has directly bonded periclase grains,

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.

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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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