Minerals Engineering 23 (2010) 273–276

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Characterization, microstructure and corrosion behavior of magnesia

refractories produced from recycled refractory aggregates
Farzin Arianpour a,*, Faramarz Kazemi b, Farhad Golestani Fard a
a
Refractories Research Division, School of Materials Engineering and Metallurgy, Iran University of Science and Technology (IUST), 16844 Narmak, Tehran, Iran
b
Hoor Mehr Sepahan Co., 81736-43513 Isfahan, Iran

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

Article history: This paper aims to report the results of some investigations carried out in Iranian steel industries to reuse
Received 30 May 2009 the spent magnesia graphite refractory bricks in the forms of the new shaped and unshaped magnesia
Accepted 3 November 2009 refractories. Economical aspects of recycling and minimizing the environmental effects of spent refracto-
Available online 2 December 2009
ries landfills were the basic goals of this research. The spent MgO–C refractory bricks from electric arc
(EAF) and ladle (LF) furnaces were analyzed in terms of microstructural and chemical properties. Differ-
Keywords: ent samples were prepared from natural sintered magnesia and 10–30 wt.% of recycled aggregates in the
Industrial minerals
forms of magnesia refractory brick and ramming mix and their physical and mechanical properties were
Crushing
Particle size
evaluated. Also the slag corrosion behavior and microstructural properties of corroded samples were
Environmental investigated. The results showed that the addition of up to 30 wt.% of recycled aggregates had no negative
Recycling effects on the properties of magnesia refractories.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction 2. Experimental procedure

Refractories are ceramic materials that are designed to with-
stand the variety of severe service conditions, high temperatures,
corrosive liquids and gases, abrasion, mechanical and thermal in-
duced stresses (Othman and Nour, 2005; Bennet et al., 1995).
Refractories are used by a variety of industries, including metal,
ceramic, cement and glass manufacturers. When refractory materi-
als have reached to end of their service life they are replaced with
new refractories that have to be manufactured from natural raw
materials and the spent refractories are typically disposed of in a
landfill wasting valuable natural resources (Fang et al., 1999; Smith
et al., 1999; Bennet and Kwong, 1997). It is understood that recy-
cling refers to use of a waste material in a manner similar to its ori-
ginal application. In contrast a waste material is typically defined
as reused when it is used differently than the original product
(Bennett et al., 2001; Conejo et al., 2006).
This paper aims to report the results of investigations carried
out in Iranian Khuzestan Steel Complex (KSCo.) by refractory re-
search division of Iran University of Science and Technology (IUST)
to reuse the spent magnesia graphite refractory bricks. The goals of
this research were characterizing spent refractories, establishing
new way for minimizing wastes and spent refractories recycling,
developing an applicable recycling technique and comparing the
properties of the recycled products with those made from virgin
material.
* Corresponding author. Tel.: +98 21 77240540x50; fax: +98 21 77240480.
E-mail address: arian@iust.ac.ir (F. Arianpour).
2.1. Spent refractories characterization
Table 1 shows the chemical analysis of intact and spent magne-
sia graphite refractory bricks which used at ladle slag line (LF & B-
LF) and EAF hot spot (EAF & B-EAF) regions. The chemical analyses
of spent bricks were measured by X-ray fluorescence method (XRF)
from hot face to 5 cm depth and the average was reported. As the
results show, the analyses of spent bricks have no significant dif-
ferences with original bricks.
2.2. Preparation of recycled aggregates
At first the penetrated layers (3–5 cm from hot face) were cut
and removed and then the none-reacted regions were crushed
and screened. The recycled aggregates from ladle were mixed with
aggregates obtained from EAF in equal weight percent. After crush-
ing, the aggregates were screened in different particle size por-
tions. In order to eliminate the residual graphite from recycled
magnesia aggregates, they were heated in a rotary laboratory scale
furnace at 1400 °C for 2 h.
2.3. Application of spent bricks in shaped refractories
In order to evaluate the using of the recycled aggregates for the
production of magnesia refractory bricks, the recycled aggregates
were added in various percents into a magnesia brick composition
as additive. Table 2 shows the particle size distribution and compo-

0892-6875/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2009.11.001
274 F. Arianpour et al. / Minerals Engineering 23 (2010) 273–276

Table 1
Chemical analysis of bricks, raw materials and slag.

Sample Carbon (graphite) SiO2 Al2O3 CaO MgO Fe2O3 MnO L.O.I
EAF 12.7 Max 0.5 Max 0.5 Max 1.2 84.7 Max 0.5 — —
LF 9.3 Max 0.5 Max 0.5 Max 1.2 90.5 Max 0.5
B-EAF 15.3 1.7 0.7 3.56 86.1 4.7 — —
B-LF 9.3 3.76 5.1 6.1 79.35 1.83 — —
Iranian 91% sintered magnesia — 4.5 1.0 3.5 91 — — 0.2
Ball clay (SQ, UK) — 53.8 30.7 0.1 0.3 — — 10.5
Microsilica (Iran Ferrosilicon Co.) — 93.6 1.32 0.49 0.97 0.87 — —
Slag — 28 13 35 6 9 9 —

Table 2
Composition and particle size distribution of magnesia bricks and monolithic refractory samples.

Composition Particle size MBM MBR10 MBR20 MBR30

Brick
Iranian 91% sintered magnesia 1–4 mm 38 28 18 8
<1 mm 30
<75 lm 32
Recycled aggregate 1–4 mm 0 10 20 30
Composition RMB RM10 RM20 RM30
Monolithic
Iranian 91% sintered magnesia 1–4 mm 40 30 20 10
<1 mm 30
<150 lm 22
Recycled aggregate 1–4 mm 0 10 20 30
Ball clay 4
Microsilica 2
Sodium hexa meta phosphate 2
Water 5

sition of designed magnesia bricks prepared from natural Iranian
sintered magnesia (91% MgO and chemical properties according
to Table 1) and recycled aggregates. Also it should be noted that
just the range of 1–4 mm (coarse grains) of recycled aggregates
were used in the samples. The reason for selecting this fraction
of particles was based on the fact that the impurities were gener-
ally gathered more in the finer fractions of recycled aggregates
than the coarser grains. Also the entrapping of impurities in coar-
ser grains lead to less negative effects on refractory properties. The
samples were mixed in a laboratory mixer with 1.5 wt.% MgCl2 as
binder and 3 wt.% water. After homogenizing and aging, the
4  6 cm cylindrical samples were shaped by hydraulic press at
100 MPa pressure. Then the samples were dried at 110 °C for
24 h and sintered at 1550 °C for 10 h in a gas furnace.
2.4. Application of spent bricks in monolithic refractories
Table 2 shows the composition and particle size distribution of
prepared refractory ramming mixes. The used binder was industri-
ally grade sodium hexa meta phosphate added in 2 wt.% dissolved
in water. The compositions were mixed in a laboratory mixer and
after homogenizing, shaped in 3  3 cm cylindrical die according to
BS 1902 (Section 7:6 – 1987) standard test method for shaping
refractory ramming mix samples. Then the samples dried at
110 °C for 24 h and heat treated in an electric furnace at 1050
and 1550 °C for 3 h.
2.5. Corrosion studies
In order to compare the corrosion resistance of natural sintered
and recycled magnesia aggregates, MBM and MBR30 samples were
selected for corrosion test study. The samples were placed in alu-
mina crucibles and the slag powder poured around them. Chemical
analysis of slag is shown in Table 1. Finally, the samples were ex-
posed to the slag at 1600 °C for 5 h in an electric furnace. Afterward
the samples were cut and the diffused and condensed regions were
investigated by scanning electron microscopy (SEM) using SEM
Tescan system at 15 keV.
3. Results and discussion
Table 3 shows the measured bulk density, apparent porosity
and cold crushing strength values from at least five brick and ram-
ming mix samples. As the results show, the mechanical strength
increases with increasing the firing temperatures. The MBM and
RBM samples had any additive and the highest CCS values. The
samples containing recycled aggregates as additive had slightly
less mechanical and physical properties than the reference samples
for both refractory monolithic and bricks. It is clear that the recy-
cled aggregates obtained from spent materials generally have
poorer strength and density. Also because of the expanded struc-
ture due to the grain adherence and the presence of micro cracks
in recycled aggregates, they will have more porosity values. Finally
it is obvious that the addition of recycled aggregates up to 30 wt.%
had no significant negative effects on the mechanical and physical
properties of refractory monolithic and bricks and the obtained
values for magnesia refractories containing recycled aggregates
are viable.
Fig. 1A shows the SEM micrograph of slag corroded MBM sam-
ple. It is obvious that during the slag/refractory reactions, the vis-
cosity of slag increases and the corrosion mechanisms become
passive in this case (Poirier et al., 2007). Also it clarifies that the
slag attacked to the sintered magnesia aggregates and dissolved
 F. Arianpour et al. / Minerals Engineering 23 (2010) 273–276 275

Table 3
Mechanical and physical properties of samples fired at different temperatures.

Temperature (°C) MBM MBR10 MBR20 MBR30

Brick
CCS (MPa) 110 12.5 12.2 12.4 12.1
1050 22 22.1 21.8 21.5
1550 45.2 38.5 38.2 36
Apparent porosity (%) 1550 16.2 18.5 18.5 20
Balk density (g/cm3) 1550 2.95 2.85 2.85 2.43
Temperature (°C) RMB RM10 RM20 RM30
Monolithic
CCS (MPa) 110 37 36 34.5 34.5
1050 29 28.5 28.5 27.5
1550 39 34 30.5 37
Apparent porosity (%) 1550 25 27 31 31.5
Balk density (g/cm3) 1550 2.85 2.8 2.78 2.6

Fig. 1. Scanning electron micrograph of (A) MBM corroded sample, (B) MBR30 fired at 1550 °C and (C) MBR30 corroded sample.

grain boundaries and finally separated periclase grains in magnesia
aggregates. Because of the presences of the large amount of impu-
rities such as CaO and SiO2 in grain boundaries, these regions are
suitable places for slag attack and have low slag corrosion resis-
tance (Lee and Zhang, 1999).
Generally magnesia graphite bricks made for steel industries
contain high quality sintered and fused magnesia. Especially fused
magnesia has high slag corrosion resistance due to its large crystal
sizes and no grain boundaries (Ebizawa, 1993; Herron and Bee-
chan, 1967). It is clear in Fig. 1B that the MBR30 sample contains
some fused magnesia aggregates with no grain boundaries. Also
the calcium silicate impurities made closed pores trapped inside
the aggregate are shown in this figure. Fig. 1C shows the micro-
structure of slag penetrated area in MBR30 sample. According to
slag/refractory interface it seems that the slag only attacks to the
bond phase. In this figure a fused magnesia aggregate is shown
near by the slag corroded zone. However it shows no magnesia
grain separation and grain boundary dissolution by slag.
significantly the amounts of refractories landfilling. The physical
and mechanical tests results of refractory brick and ramming mix
samples containing recycled aggregates showed that the addition
of up to 30 wt.% of recycled aggregates had no negative effects
on the properties of magnesia refractories. Also the corrosion
behavior of sample containing recycled aggregates was slightly
better than the samples made from natural sintered magnesia.
Acknowledgments
The authors wish to express their appreciation for the helpful
financial and technical supporting of this work by Iran University
of Science and Technology (IUST) and Iranian Khuzestan Steel
Complex (KSCo.).
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The quantity of spent refractories produced from Iranian steel-
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