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90 INTERCERAM – REFRACTORIES MANUAL I/2014

Review PaPeRs

Soumya Mukherjee*, S. Pramanik*, Siddhartha Mukherjee*

A Comprehensive Review of Recent


Advances in Magnesia Carbon Refractories
The auThor absTracT Keywords

The corresponding author, The paper describes state of the art developments in the formulation of MgO−C refractories,
Soumya Mukherjee, has a MgO−C refractories, products that have been an integral part of the iron nano carbon, mechanical
Master Degree in Industrial and steel industry over the last two decades. The effects of important properties, GONs,
Metallurgy. He is currently techniques and variations in operational parameters are reviewed and thermochemistry,
pursuing his Ph.D. research in summarized, including the impact of antioxidants on oxidation behaviour, microstructure, Fig. 1 •
the field of electronic com- incorporation of graphite or nano carbon content, and the influence of Young’s modulus at 130
posite materials. His further electromagnetic fields on slag corrosion resistance. Most of the major INTERCERAM 63 (2014) [3]
research interests include experimental findings related to properties of MgO−C refractories are a
refractory, waste recycling and engineering, ad- focus of the article. It addresses the oxidation kinetics of magnesia • bet
vance ceramics and composite, as well as char- carbon refractory bricks, the microstructure of graphite and nano car- env
acterization techniques. He has published in bon-containing MgO−C refractories, determination of the mineralogical These
several peer-reviewed international journals and composition of MgO−C refractories by the Rietvelt method, and the of ext
became an associate member of the Indian In- mechanical behaviour of these refractories.
stitution of Engineers in 2012. At present he
MgO−
is visiting faculty member of the Department dresse
of Ceramic Technology, Government College of mater
Engineering and Ceramic Technology. of the
E-Mail: smmukherjee3@gmail.com tigatio
this p

2 Pre
1 Introduction refractory together. Since the slag in steel- etration resistance [3, 4]. Graphite also has brick
Refractory materials are non-metallic in- making is predominantly basic in nature, lubricating properties due to the presence of MgO−
organic substances that are capable of with- refractories are also basic. They are widely weak van der Waals inter-layer bonds. But a stan
standing very high temperatures. According used for steelmaking applications, e.g. the carbon suffers from poor oxidation resist- M. Ba
to ASTM C71 the definition of refractories lining of basic oxygen furnaces, steel ladles, ance. It may be oxidized to form CO or CO2, witho
is “non-metallic materials having those chem- LD converters, electric arc furnaces, and ap- which results in a porous structure having mixed
ical and physical properties that make them plications in secondary steelmaking. These poor strength and reduced corrosion resist- form
applicable for structure or as components of refractories have been dominant along the ance. Adding large amounts of carbon also seque
systems that are exposed to environments slag line of ladles for at least a decade due to leads to more heat loss through the refrac- The m
above 1000 °F / 538 °C” [1]. Some salient at- the properties which are contributed by tory and causes higher shell temperatures 2 h. T
tributes that one can associate with these MgO and carbon. Clean steel can be pro- on steel vessels. Shell deformation then in- pressi
materials are excellent mechanical proper- duced with less refractory consumption by creases, leading to reduction of ladle life. dimen
ties both at room temperature and high using MgO−C bricks [2]. These refractories Greater carbon percentage also leads to in- The
temperature, the ability to withstand rapid enjoy a very significant advantage over creased carbon pick-up by steel which is with m
temperature fluctuations due to repeated Al2O3-based and SiO2-based materials since undesirable since steelmaking is normally a 200 M
heating and cooling during application as a the melting point of magnesia is 2800 °C. decarburization process. Another result is quent
lining material in iron and steel converters, Moreover, a reaction between MgO and C more CO and CO2 gas by-product, a rising to rem
and good resistance to corrosion and ero- leads to the nascent formation of a dense concern for the global environment. These binde
sion due to molten metal, slag, etc. Magnesia layer of MgO at the working surface of the factors have necessitated efforts to reduce shape
carbon refractory can be described as a MgO−C brick. This layer restricts penetra- the total amount of carbon used in MgO−C
composite material based on MgO and C. It tion of slag and metal and promotes cor- materials without sacrificing their major 3 Ox
is used either in the form of bricks or casta- rosion resistance. Unfortunately, MgO has beneficial properties. Use of nano carbon Due t
bles. The constituents of magnesia carbon poor thermal shock resistance. In contrast, has been found to be an effective solution to MgO−
bricks are: magnesia grains, which are the graphite has high thermal conductivity, low this problem. high
main component, graphite, antioxidants to thermal expansion and better spalling re- Some of the challenges driving improve- have
protect the carbon from getting oxidized sistance. To overcome the shortcomings of ment of MgO−C refractories are closely A.S. G
and high carbon-containing pitch or resin MgO, graphite was added to MgO matrix to linked with future significant technological variou
as a binder to keep the different parts of the create a new high temperature material with advances in the manufacturing of iron and ance o
improved properties. Carbon fills the po- steel, including: oxida
rous structure of the MgO matrix and, by • higher furnace capacities, Their
* Department of Metall. and Mater. Engineering, virtue of its non-wetting character, helps to • increases in operating and hot metal tem- were i
Jadavpur University, Kolkata-700032 (India) improve slag and metal corrosion and pen- peratures, and 1

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INTERCERAM – REFRACTORIES MANUAL I/2014 91

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1 2

es
s

s,
hanical

Fig. 1 • Carbon loss of MgO–C specimens with/without 3 mass-% antioxidant Fig. 2 • Carbon loss of MgO–C specimens with/without 3 mass-% antioxidant
at 1300 °C [5] at 1500 °C [5]
14) [3]

• better manufacturing and application and 6 h). Carbon loss of the bricks as a by formation of MgAl2O4 spinel phase, and
environments. weight percentage was used as the measure bricks containing Si and SiC showed im-
These factors have contributed to the launch of oxidation resistance (Figs. 1−2). XRD, proved oxidation resistance due to presence
of extensive research work in the field of SEM and EDS characterization analyses of of Mg2SiO4 forsterite. Each of these phases
MgO−C refractories. Researchers have ad- oxidized areas of the bricks were performed was confirmed by XRD and SEM analysis.
dressed diverse topics that aim toward better to observe phase changes and gather micro- These layers on brick surfaces prevent in-
material properties and applications. Some structural information. Oxidation resistance gress of oxygen, which results in better oxi-
of the interesting revelations of these inves- with B4C was improved due to formation of dation resistance (Figs. 3−4). The reduction
tigations are reviewed in the remainder of an Mg3B2O6 layer on the brick surface. Simi- in oxidation at 1500 °C was found to be
this paper. larly oxidation of bricks with Al was reduced better than at 1300 °C. The reasons for this

2 Preparation of magnesia carbon


o has bricks
nce of MgO−C materials are prepared by following
s. But a standard sequence of steps. For example,
resist- M. Bag et al. [8] prepared samples with and

Material testing
r CO2, without nano carbon. Raw materials were
having mixed thoroughly inside a pan mixer to
resist- form a homogeneous mixture. The mixing machines
n also
efrac-
sequence of ingredients is shown in Table 1.
The mixed batches were then aged for about
Quality control
atures 2 h. This was followed by uniaxial hydraulic Compression test
en in- pressing in a steel mould to form bricks of
Bending test
e life. dimension 220 mm × 110 mm × 75 mm.
to in- The compaction involved twelve strokes Tensile test
ich is with maximum specific pressure of around
mally a 200 MPa. The pressed shapes were subse-
ult is quently tempered in a kiln at 200 °C for 12 h
rising to remove volatiles and polymerized organic
These binder, and impart strength to the pressed
educe shapes.
gO−C
major 3 Oxidation behaviour
arbon Due to the poor resistance of carbon, the
ion to MgO−C bricks tend to oxidize, especially at
high temperatures. Various antioxidants
prove- have been used to suppress this problem.
losely A.S. Gokce et al. [5] studied the effect of
ogical various antioxidants on the oxidation resist-
n and ance of MgO−C bricks. Four different anti-
oxidants were used: Al, Si, B4C and SiC. FORM+TEST Seidner&Co. GmbH
Their oxidation effects on MgO−C bricks phone +49 (0) 7371 9302-0
l tem- were investigated at temperatures of 1300 °C sales@formtest.de
and 1500 °C and as a function of time (2, 4 www.formtest.de

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92 INTERCERAM – REFRACTORIES MANUAL I/2014

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3 4 Indire
where
MgO.
C(s) +

This r
above
Their
ture r
oxida
tors t
tion w
• par
Fig. 3 • Oxidized areas of MgO–C specimens after 6 h oxidation at 1300 °C: Fig. 4 • Oxidized areas of MgO–C specimens after 6 h oxidation at 1500 °C: • acc
(a) with/without 1 mass-% antioxidant, (b) with/without 3 mass-% antioxi- (a) with/without 1 mass-% antioxidant, (b) with/without 3 mass-% antioxi- gra
dant [5] dant [5] • deg
• sha
5 6 • flow
aro
• reac
The p
five d
• inw
airf
• inw
rou
face
• che
O2 a
• out
por
Fig. 5 • TG oxidation curves of carbon sources in a non-isothermic regime [6] Fig. 6 • DTG oxidation curves of carbon sources in a non-isothermic regime [6] inte
• out
sam
behaviour differed for the different antioxi- In another study, V.G. Rocha et al. [6] com- uble particles that inhibit the growth of mo
dants. Al-containing bricks formed greater pared the oxidation resistance of different mesophase spheres by surrounding any Math
amounts of spinel phase at 1500 °C than at carbon sources in MgO−C materials, in- structures formed during carbonization. explai
1300 °C. The better oxidation resistance of cluding graphite (which acts as the chief Petroleum pitch coke, on the other hand, i.e. th
bricks with B4C at 1500 °C was due to the source of carbon in MgO−C bricks), carbon was devoid of these particles, so mesophase
1360 °C melting point of Mg3B2O6. Mg3B2O6 black, and petroleum and coal tar pitch carbon aggregate growth was not similarly Tabl
is a very good oxygen barrier above its melt- binder materials. The order of air reactivity restricted (Fig. 7). The study concluded that MgO
ing point. Liquid Mg3B2O6 fills open pores was graphite < petroleum pitch coke < coal petroleum pitch coke can be a desirable Prop
and forms a thin film layer on brick surfaces tar pitch coke < carbon black (Figs. 5−6). substitute for conventional coal tar pitch as
App
at 1500 °C so oxygen cannot diffuse into the Variation in the respective carbon structures a brick binder material since it is less reac-
Bulk
refractory. For the remaining two antioxi- was cited as the main reason behind this tive to air.
Cold
dants Si and SiC, the reason for greater oxi- behaviour. Graphite has a well-ordered
dation resistance at 1500 °C was the forma- structure, whereas carbon black is an amor- 4 Oxidation kinetics HMO
tion of more CO. This led to more SiO2, phous material made up of small spheres Since oxidation is a major cause of degrada- Oxid
which favours stable forsterite formation. Of (size < 1µm) which tend to agglomerate to tion of MgO−C based brick properties, Slag
the antioxidants, B4C was found to be the form aggregates of about 20−50 µm. Coal M.A.F. Sani et al. [7] conducted a detailed Ther
most effective, followed by Al. Si was next tar pitch coke consists mainly of anisotropic study of the rate/kinetics of oxidation and
best, followed by SiC, which was better than microstructures of smaller size. This is due disappearance of graphite. Oxidation occurs
bricks without any presence of antioxidant. to the presence of primary quinolone-insol- in two ways: Tabl
Direct oxidation or gas phase oxidation, L0, L
Table 1 • Sequence of mixing for the constituents of MgO–C refractory [8] where carbon is consumed by gaseous oxy- Raw
Steps Mixing sequence Mixing time / min
gen. Fuse
1 Coarse and medium MgO 1.0 2C(s) + O2(g) → 2CO(g) (1) Grap
Add graphite, Al metal powder, pitch powder and nano Anti
2 4.0 This is the major mechanism of oxidation
carbon black CB S
at temperatures less than 1400 °C and is
3 Add liquid resin 8.0 commonly used to compare the oxidation CB N
4 Add fine MgO powder 12.0 resistance of refractories. Phen

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4 Indirect oxidation or solid phase oxidation,


7
where carbon reacts with oxygen in solid
MgO.
C(s) + MgO(s) → CO(g) + Mg(g) (2)

This reaction is important for temperatures


above 1400 °C.
Their study was carried out in the tempera-
ture range from 1000 to 1200 °C, so only Fig. 7 • Optical micro-
oxidation due to air was explored. The fac- scopy images of coked
tors that affected the rate of direct oxida- material obtained from
(a) coal-tar pitch and
tion were:
(b) petroleum pitch
• partial pressure of oxygen,
containing refractories
°C: • accessibility of oxygen to the edges of
[6]
oxi- graphite flakes,
• degree of open porosity,
• shape and orientation of products, tions of mass transfer, relations were ob- ing strength (CCS), hot modulus of rupture
• flow characteristics of gaseous species tained connecting radius of unoxidized (HMOR), oxidation resistance, static slag
around products, area, oxidation time and different physical corrosion resistance, thermal shock resist-
• reactivity of the flakes. and kinematic parameters. ance, and distribution of carbon and pore
The process of oxidation was divided into sizes. Among the various samples the opti-
five different steps: 5 Effect of introduction of nano mum set of attributes was observed for the
• inward mass transport of O2 from bulk carbon batch containing 0.9 mass-% of nano car-
airflow to the sample surface, Carbon brings several beneficial properties bon. This batch was then compared to
• inward diffusion of O2 through the po- to MgO−C materials. But it has detrimental samples without any nano carbon. The
rous oxidized layer from the sample sur- effects as well, so excess carbon should be properties of the two batches were more or
face to the reaction surface, avoided. 10−18 % carbon is generally incor- less the same, and in some cases, even better
• chemical reaction between graphite and porated in these materials. But this amount for the batch containing nano carbon. They
O2 at the reaction interface, can be drastically reduced without sacrific- concluded that the total carbon content of
• outward diffusion of CO through the ing beneficial properties if nano carbon MgO−C bricks could be lowered signifi-
porous oxidized layer from the reaction replaces some of the bulk graphite. cantly without sacrificing their beneficial
me [6] interface to the sample surface, M. Bag et al. [8] mixed varying amounts properties through substitution of nano
• outward mass transport of CO from the (0.3, 0.6, 0.9, 1.2 and 1.5 mass-%) of nano carbon. This was possible due to better
sample surface into the surrounding at- carbon in the form of amorphous carbon dispersion of nano carbon in the MgO
th of mosphere. black together with 3 mass-% graphite in matrix. An extensive comparison of the
g any Mathematical models were developed to MgO and compared the resulting samples. properties of their MgO−C refractory sam-
ation. explain the extent of oxidation with time, The different properties they evaluated were ples with and without nano carbon is shown
hand, i.e. the kinetics of the process. From equa- apparent porosity, bulk density, cold crush- in Table 2.
phase A fairly similar work was carried out by
milarly Table 2 • Comparison of the properties of conventional MgO−C refractories and L. Bo et al. [9]. Due to the various detrimen-
d that MgO−C refractories containing nano carbon (batch T-4) [8] tal effects of conventional carbon use, one
irable Property Batch T-4 Batch T-C
may be tempted to bring down the total car-
tch as bon content. But the thermal shock resist-
Apparent porosity / % 4.3 3.8
reac- ance of MgO−C bricks is significantly re-
Bulk density / g/cm3 3.12 3.05
duced with reductions in the amount of
Cold crushing strength / MPa 51 37.5
graphite, restricting their possible practical
HMOR / MPa 4.5 3.9 applications. The researchers attempted an
grada- Oxidation loss / % 21.82 36.95 innovative solution to the problem by also
erties, Slag penetration depth / mm 2.01 1.98 employing nano carbon in MgO−C refracto-
tailed Thermal shock resistance / cycle 12 12 ry. Two varieties of nano carbon were used:
n and
occurs
Table 3 • Raw material formulations of low-carbon samples
Table 4 • Physical properties of the samples (L0, L1, L2) [9]
ation, L0, L1 and L2 (in mass-%) [9]
s oxy- Raw materials L0 L1 L2 Property L0 L1 L2
Fused magnesia 96 96 96 Bulk density / g/cm3
3.11 3.14 3.14
(1) Graphite 1.4 1 1
Apparent porosity / % 5.7 4.3 4.2
Antioxidants 3 3 3
dation CCS before coking / MPa 81.8 88.6 96.6
CB SRFB – 0.4 –
nd is MOR before coking / MPa 21.6 23.7 25.8
dation CB N220 – – 0.4
Phenolic resin 3.5 3.5 3.5 MOR after coking / MPa 7.1 7.9 8.7

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Makin
8 9 SiO2–
of spi
in agr
necess
nel la
tion o
presen
greate

8 Eff
Fig. 9 • SEM images of corroded low carbon MgO–C refractories by slag (a) under EMF and (b) EMF free. X. Li
(M) magnesia, (MP) metal particles, (C) graphite, (S) solid solution, (SP) spinel [12] aspec
refrac
10 effect
the sla

Fig. 8 • Spinel layer formed at slag/refractory


interface: (a) backscattered electron images of
Mg(Cr,Al)2O4 spinel layer. (Per) periclase, (SI) infil-
trated slag, (Mp) precipitate of Cr-rich metal, (Sp)
spinel layer, (CMS) CaOMgOSiO2; (b) concentration
profiles along the line A–B in the BSE image [11]

a) semi-reinforcing furnace black (SRFB)


and
b) CB N220.
The composition of the raw materials in the
samples with low carbon content and their
physical properties are summarized in
Tables 3 and 4. The CB N220 sample was
found to have the best thermal shock resist-
ance. The addition of carbon black N220
enabled MgO−C to endure much greater
thermal stress. Better dispersion of nano
carbon black in the MgO−C matrix results Fig. 10 • SEM images of the interface for corroded low carbon MgO–C refractories: (a) in an electro-
in a decrease in elastic modulus value and magnetic field, (b) electromagnetic field-free, (c) the corresponding EDS pattern of point MF [12]
an increase in thermal shock resistance. The
total amount of carbon was reduced to less amount of nano carbon fixed at 0.9 mass-%, 7 Interaction with slag
than 3 % without adverse effects. the effect of variation in graphite content M. Guo et al. [11] performed experiments
was studied through samples containing 1, on pitch-bonded MgO−C refractory to
6 Effect of graphite content 3, 5, 7 and 9 mass-% graphite. The batch study its corrosion behaviour. The material Fig. 12
Although use of nano carbon as a substitute containing 3 mass-% graphite was found to was subjected to an Al2O3 rich (~15 mass-%) (f) dum
for graphite in MgO−C refractories shows have optimal properties. As graphite content slag from stainless steelmaking. Rotating fin-
tremendous promise, it cannot completely increased up to 3 mass-%, uniform distribu- ger tests were carried out in a VOD furnace
replace flake graphite. Amorphous nano tion of carbon particles in the matrix phase at high temperature (>1650 °C) and low ries. T
carbon black produces inferior oxidation was achieved, resulting in good filling of oxygen partial pressure (1.5–4.3∙10–10 atm). rosion
resistance and thermal conductivity com- intergranular voids. The results indicated Microstructural characterization (Fig 8) of the sl
pared to graphite flakes, and these proper- improvement of porosity and densification the worn samples revealed significant corro- 0.8. M
ties are also primary requirements for strength at both room and high tempera- sion of MgO−C bricks used in the slag line carrie
MgO−C refractories. Hence the amount of tures. Additional graphite does not yield of VOD ladles. Slag infiltration and MgO a) an
graphite used in combination with nano improved occupation of voids and results dissolution increased when temperatures b) a re
carbon remains an important parameter. So in slightly inferior properties. The elemental were higher and with greater exposure time Vario
M. Bag et al. [10] as an extension of the mapping of carbon also showed higher con- of the refractory. The conditions for the ing s
work described above also investigated the centration of carbon, due to the presence formation of a passivating spinel layer which Figs. 9
effect of variations of graphite content in of nano carbon, than conventional MgO−C reduces slag corrosion were also studied in and e
nano carbon-containing MgO−C refracto- refractories. This result supports the choice this work. Problems with the reaction be- were
ry. They found that a low carbon MgO−C of graphite content fixed at 3 mass-% for the tween MgO and C had been cited as the struct
batch containing 0.9 mass-% of nano car- work in which nano carbon content was main cause of poor behaviour for these an ele
bon yielded optimum properties. With the varied. materials under simulated VOD conditions. spinel

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Making use of a quarternary CaO–MgO– Fig. 11 • XRD patterns


9 SiO2–Al2O3 phase diagram, the temperature of slag corroded low
11
of spinel formation was found to be 1500 °C, carbon MgO–C refrac-
in agreement with experimental results. A tories under EMF and
necessary condition for formation of a spi- EMF-free conditions
[12]
nel layer to bring down the rate of dissolu-
tion of MgO in VOD conditions was the
presence of more than 25 mass-% Al2O3 and
greater than 20 mass-% MgO.

8 Effect of an electromagnetic field


free. X. Li et al. [12] explored an interesting
aspect of the interaction between MgO−C
refractories and slag. The work studied the
effect of electromagnetic fields (EMF) on
the slag corrosion resistance of the refracto-

12

o-

ments
ry to
aterial Fig. 12 • Morphology of commercially available binder system with added TiO2 and Al: (a) amorphous whiskers, (b) AlN, (c) Al4C3, (d) carbide whiskers, (e) TiCN,
ss-%) (f) dumbbell shaped whiskers [14]
ng fin-
rnace
d low ries. The MgO−C material subjected to cor- interfacial layer. Also present was monticel- oxide in the slag and carbon in the refracto-
atm). rosion tests contained 6 mass-% carbon and lite (CaMgSiO4) in solid solution and some ries. Under EMF conditions, slag corrosion
8) of the slag had basicity (CaO/SiO2) of about MnO and FeO. In the EMF-free furnace, and oxidation of low carbon MgO−C re-
corro- 0.8. Melted slag resistance experiments were MgFe2O4 spinel was absent from the inter- fractories increases.
g line carried out in two different furnaces: facial layer, which contained monticellite Another effect of EMF was addressed by
MgO a) an induction furnace with EMF, (CaMgSiO4) solids. At high temperatures, the same research group in a related tech-
atures b) a resistance furnace devoid of EMF. EMF increases the diffusion coefficient of nical research article that discussed possi-
e time Various characterization techniques includ- Fe2+/3+ ions, which displaces Mg2+ to form ble explanations for high corrosion rates
or the ing scanning electron microscope (SEM, MgFe2O4 and Mn ions. Intense stirring of [13]. In resistance furnaces (absent EMF),
which Figs. 9−10), X-ray diffraction (XRD, Fig. 11), molten steel and slag in the presence of EMF recrystallisation and growth of secondary
ied in and energy dispersive X-ray analysis (EDX) increases the wear of low carbon MgO−C MgO results in formation of a dense layer
n be- were used to analyse the resultant micro- and the thickness of the erosion layer de- of MgO that promotes better corrosion
as the structures. In the induction furnace with creases in the refractory. More slag pene- resistance against basic slag generated by
these an electromagnetic field (EMF), MgFe2O4 trates into the refractories and leads to standard or alloy steelmaking processes.
tions. spinel and Mn ions were generated in the further reduction reactions between metal EMF increases the rate of dissolution of

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Fig. 13 • Rietveld plot the thermodynamically interpreted phases tainin


13 (20–80 °/2) for Mg-C against actual microstructures. At 1200 and As a r
refractory with the 1500 °C, addition of Al led to the formation erode
main peaks of each of AlN whiskers, Al2O3 and Al4C3 shells sur- was o
phase labelled. rounding porous cores at the location of the and B
Observed (crosses), original Al particles, and fine precipitate forme
calculated (line) and
magnesium aluminate spinel in the matrix ing. It
difference (bottom line)
and as a surface layer on MgO aggregates. and g
powder patterns are
shown; the marks cor-
Gaseous species such as Al were present tween
respond to the Bragg during the formation of these phases. crysta
peaks of the different When Si is added, the phases that form at carbo
phases, from bottom to 1200 °C are SiC, Si3N4 and SiO2, either di- was n
top: MgO, C (graphite), rectly as a layer on Si particles or indirectly slight
Al2O3, SiC, Si, Al and as a shell around a SiC core, and forsterite MgO.
AlPO [17] in the form of fine precipitates in the ma- remai
trix and as a layer on MgO aggregate sur- rior co
faces. Of these phases, only Si3N4 is not
thermodynamically stable at 1500 °C. Gas- 10 D
MgO and decreases the pressure of the Mg analyse microstructure and phase content. eous species including SiO were involved comp
vapour bubble, thereby preventing forma- Mechanical properties and oxidation resist- in evolution of the phases. 3MgO∙B2O3 A.G. d
tion of a dense MgO layer. This effect in- ance were also studied, including cold formed with use of the B4C antioxidant. It diffrac
creases the rate of refractory corrosion in compression strength, open porosity after liquefies above 1350 °C. Gaseous species metho
induction furnaces. coking and oxidation depth after exposure such as B2O3 were present during the for- tories
to air atmosphere for 3 h at 1200 °C. Addi- mation of 3MgO∙B2O3. comp
9 The effect of introduction of Al tion of TiO2 and TiO2/Al resulted in forma- S. Zhang et al. [16] also examined the influ- graph
and TiO2 on the microstructures tion of TiCN and TiC, respectively (Fig. ence of additives on the corrosion resistance SiC, 0
of MgO−C refractories 12). The mechanical strength, oxidation re- and microstructures of MgO−C refracto- AlPO
The role of antioxidants in inhibiting car- sistance and abrasion resistance of the ries. Oxidation of carbon and dissolution of These
bon oxidation of MgO−C refractories by bonding matrix were improved as a result. MgO by slag were affected in various pat- charac
reducing CO to C was explained earlier in Enhanced interlocking mechanisms in the terns by the presence of antioxidants. Tests dated
the article. Antioxidants also improve the bonding matrix explain the superior ther- were performed against slag with CaO : SiO2 powd
mechanical properties and microstructure mal shock resistance. AlN was found to be mass ratio = 1.38 in a model EAF at 1650 °C to dire
of MgO−C bricks. present only at the interface of the carbon for 30 h. Addition of Al increased the oxi- tion o
C.G. Aneziris et al. [14] studied the high matrix and the Al grains. dation resistance of carbon slightly, but the
temperature interactions and phase evolu- In another work, S. Zhang et al. [15] studied effect was overshadowed by an increase in 11 M
tion of a commercially available binder sys- the thermochemistry and microstructures MgO dissolution. Overall improvement of N. Sc
tem based on liquid phenolic resin and a of refractories formulated with various anti- corrosion resistance was therefore not sig- chani
high melting coal tar resin powder with oxidants. The investigation was divided into nificant. Addition of Si or Al + Si led to tories
added TiO2 and Al. Characterization tech- two parts. Thermodynamic calculations worse corrosion resistance due to an even Young
niques such as X-ray diffraction (XRD), were initially performed on the phases ex- greater increase in MgO dissolution. Use of define
scanning electron microscope (SEM), ener- pected from firing of MgO−C refractories B4C resulted in the worst corrosion resist- were
gy dispersive X-ray (EDX), and electron at 1200 and 1500 °C with Al, Si and B4C ance since dissolution of MgO was greatly pitch-
backscatter diffraction (EBSD) were used to antioxidants. The researchers then validated increased by the presence of a boron-con- differe
the m
loadin
Table 5 • Specification of materials (in mass-%) for mechani- Table 7 • Tensile properties of the materials [19] found
cal property testing [19] Property Material A Material B linear
Materials composition Material A Material B Young’s modulus / GPa 25.2 69.8 elastic
MgO 82.9 91.4 Tensile strength / MPa 6.5 6.3 below
CaO 1.3 1.1 ured
Maximum strain 5∙10–4 1.64∙10–4
SiO2 0.7 ~0 bend
Al2O3 0.6 ~0 Differ
Table 8 • Absolute compression strength to tensile strength
C 13.1 5.6 were
ratio [19]
ment
Density / g/cm3 2.83 3.07 Property Material A Material B H. Ba
Ratio 4.2 16.3 behav
Table 6 • Compression properties of the materials. [19]
BOF
Property Material A Material B
Table 9 • Tensile properties measured by bend test [19] under
Young’s modulus / GPa 10.6 102
Property Material A Material B With
Poisson’s ratio 0.16 0.24 sonic
Compression strength / MPa -27.2 -115.6 Young’s modulus / GPa 18.6 69
termi
Maximum strain -4.9∙10–3 -1.62∙10–3 M.O.R / MPa 7.4 13.5 range

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phases taining liquid formed inside the refractory.


0 and As a result, carbon in the matrix was easily 14
mation eroded by slag. The best corrosion resistance
s sur- was obtained from refractory containing Al
of the and B4C. A boron-containing liquid was
pitate formed that prevented carbon from oxidiz-
matrix ing. It also increased the rate of formation
gates. and growth of MgAl2O4 spinel crystals be-
resent tween carbon elements in the matrix. These
hases. crystals play an important role in preventing
rm at carbon oxidation and erosion. The carbon
er di- was not easily washed away in spite of a
rectly slight increase in the rate of dissolution of
sterite MgO. This allowed the refractory texture to
e ma- remain intact, which accounted for its supe-
e sur- rior corrosion resistance.
s not
Gas- 10 Determination of chemical
olved composition
Fig. 14 • Different SEM images of MgO–GON composite powders [21]
∙B2O3 A.G. de la Torre et al. [17] used X-ray powder
ant. It diffraction techniques coupled with Rietveld
pecies methodology to characterize MgO−C refrac- values varied strongly between the two tem- binder. At higher temperatures it was main-
e for- tories. Their test refractory was found to be perature limits. This variation was con- ly affected by the metallic additives.
composed of 68.3 mass-% MgO, 8.1 mass-% firmed by XRD, SEM and EDS analyses. The T. Zhu et al. [21] explored the microstruc-
influ- graphite, 13.5 mass-% Al2O3, 4.4 mass-% investigators concluded that oxidation of ture and mechanical properties of MgO−C
stance SiC, 0.6 mass-% Si, 1.2 mass-% Al, 1.5 mass-% carbon heated in air, particularly between refractories that contained graphite oxide
racto- AlPO4 and 2.4 mass-% silicone (Fig 13). 600 to 800 °C, resulted in a decrease in value nano (GON) sheets. A composite powder of
ion of These results were cross-checked using other of the average Young’s modulus by approxi- MgO and GON was first prepared through
s pat- characterization procedures. The work vali- mately 10 %. At temperatures higher than ball milling of expanded graphite and mag-
Tests dated the Rietveld method along with X-ray 1100 °C, sintering of MgO grains into aggre- nesia powders. This mixture was then incor-
: SiO2 powder diffraction as a suitable methodology gates can lead to a drastic increase of Young’s porated into conventional MgO−C refracto-
650 °C to directly obtain the mineralogical composi- modulus by around 130 %. ries. XRD, SEM and EDS characterization
e oxi- tion of MgO-graphite refractories. L. Musante et al. [20] conducted an exten- and three-point bending and thermal shock
ut the sive study of the mechanical behaviour of tests were applied to study the phase com-
ase in 11 Mechanical behaviour MgO−C refractories. Two different types of position, microstructure, and thermo-me-
ent of N. Schmitt et al. [18] investigated the me- materials were used, one with resin as the chanical properties of the refractory materi-
ot sig- chanical behaviour of MgO−C based refrac- binder and the other using pitch. Various als. The investigation confirmed uniform
ed to tories. The main parameters addressed were metallic additives were also present. Tests distribution of GONs of different sizes and
even Young’s modulus and tensile strength. As were performed at high temperatures in a thicknesses in the magnesia matrix (Fig. 14).
Use of defined in Table 5, two types of materials non-oxidizing atmosphere. Prior to the ac- It also revealed that the GONs made a
resist- were examined: resin-bonded (A) and tual mechanical tests, the materials under- significant improvement in the material’s
reatly pitch-bonded (B) MgO−C refractories. The went a detailed characterization involving high temperature mechanical properties.
-con- differences in mechanical performance of mineralogical analysis by XRD coupled with This was mostly due to the GONs strength-
the materials under tensile and compressive the Rietveld method, differential thermal ening and toughening the MgO−C refracto-
loading are shown in Tables 6−8. They and thermogravimetric analysis, measure- ry and by in-situ formed ceramic phases in
found that the stress-strain curve was non- ments of apparent porosity and bulk density, the matrix.
B linear even for very low strain values. The and SEM microstructure imaging. Mechani-
elastic domain was limited to strain values cal tests were performed with an Instron 12 Conclusions
below 10–5. Tensile properties were meas- 8501 servohydraulic fatigue testing machine. The main results of this research review of
–4 ured by a specially designed three-point A constant displacement of 0.1 mm/min was recent advancement in the field of MgO−C
bend test. The results are shown in Table 9. applied until specimen failure occurred. based refractories can be concisely summa-
Differences between the two sets of tests Stress-strain curves under compression in rised. B4C was the most effective antioxi-
th
were explained with the help of finite ele- N2 atmosphere were plotted for room tem- dant. Intensity of air reactivity for different
ment method modelling. perature, 600, 1000 and 1400 °C. Failure carbon-based refractory compositions was
B H. Baudson et al. [19] studied the elastic stress, failure strain, yield stress and Secant observed to be: graphite < petroleum pitch
behaviour of MgO−C refractories used in a Young’s modulus were calculated from the coke < coal tar pitch coke < carbon black.
BOF up to temperatures around 1400 °C stress strain curves. The resin-bonded mate- This is a consequence of the degree of or-
under air and inert atmospheric conditions. rial displayed higher mechanical property dered variation present in the respective
B With the help of a high temperature ultra- values and Young’s modulus over the entire structures. Two types of oxidation kinetics,
sonic technique, Young’s modulus was de- range of testing temperatures. Up to 1000 °C, direct and indirect oxidation, were found to
termined for materials in the temperature the mechanical behaviour of the MgO−C be influenced by factors like O2 partial pres-
range from 700 °C to 1400 °C. The measured refractories was controlled by the type of sure, the porosity, shape and orientation

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of products, and graphite flake reactivity. 600−800 °C. Sintering of MgO grains at [8] Bag, M., Adak, S., Sarkar, R.: Study on low carbon
0.9 mass-% nano carbon with 3 mass-% 1100 °C leads to a drastic increase of containing MgO−C refractory: Use of nano carbon.
Ceram. Inter. 38 (2012) 2339–2346
graphite in MgO provides optimum appli- Young’s modulus by 130 %. Mechanical [9] Bo, L., Jia-lin, S., Guang-sheng, T., Kai-qi, L., Lin,
cation properties. Higher additions of test at high temperature in non-oxidizing L., Yong-feng, L.: Effects of nanometer carbon black
graphite result in inferior performance due atmosphere revealed that up to 1000 °C, on performance of low-carbon MgO−C composites.
J. Iron and Steel Res. Inter. 17 (2010) 75–78
to lack of better yields in void packing. the mechanical behaviour of MgO−C re- [10] Bag, M., Adak, S., Sarkar, R.: Nano carbon contain-
Chemical analysis of MgO−C can be per- fractories is governed by the type of binder. ing MgO−C refractory: Effect of graphite content.
formed and optimized using Rietveld XRD Resin-bonded material generally displayed Ceram. Inter. 38 (2012) 4909–4914
[11] Guo, M., Parada, S., Jones, P.T., Dyck, J.V., Boydens,
techniques. Rotary slag tests determined better Young’s modulus and other mechan- E., Durinck, D., Blanpain, B., Wollants, P.: Degrada-
that slag corrosion is reduced and the rate of ical attributes than pitch-based. At higher tion mechanisms of magnesia-carbon refractories
MgO dissolution decreases when passivat- temperatures mechanical properties are by high-alumina stainlesssteel slags under vacuum.
Ceram. Inter. 33 (2007) 1007–1018
ing spinel layers were formed. Spinel for- mainly affected by any metallic additives in [12] Li, X., Zhu, B., Wang, T.: Effect of electromagnetic
mation is possible in the presence of great- the refractory. Proper distribution of field on slag corrosion resistance of low carbon
er than 25 mass-% Al2O3 and 20 mass-% graphite oxide nano (GON) sheets leads to MgO–C refractories. Ceram. Inter. 38 (2012) 2105–
2109
MgO. In the presence of EMF, MgFe2O4 significant improvement in the high tem- [13] Li, X., Zhu, B., Wang, T.: Electromagnetic field ef-
spinel with some Mn content was generat- perature properties of MgO−C due to its fects on the formation of MgO dense layer in low
ed in the MgO−C refractory interfacial lay- strengthening and toughening mechanisms carbon MgO–C refractories. Ceram. Inter. 38 (2012)
2883–2887
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tion. In the absence of EMF, MgFe2O4 was able ceramic phases within the matrix. structure evaluation of MgO–C refractories with
absent and monticellite was formed. Addi- TiO2- and Al-additions. J. Eur. Ceram. Soc. 27
(2007) 73–78
tion of TiO2 and Al together with coal tar [15] Zhang, S., Marriott, N.J., Lee, W.E.: Thermochemis-
resin results in improved mechanical References try and microstructures of MgO−C refractories con-
strength, oxidation resistance and abrasion [1] Annual book of ASTM standards, Refractories: Ac- taining various antioxidants. J. Eur. Ceram. Soc 21
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(2003)
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[3] Figueiredo Jr, A., Bellandi, N., Vanola, A., Zamboni, 2393–2405
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I.: Technological evolution of magnesia-carbon
dissolution of MgO was observed. The me- bricks for steel ladles in Argentina. Iron and Steel mineralogical composition of a MgO–C refractory
chanical behaviour of MgO−C was ana- Technol. 1 (2004) 42–47 material obtained by Rietveld methodology. J. Eur.
[4] Buchebner, G., Sampayo, L., Samm, V., Blondot, P., Ceram. Soc 26 (2006) 2587–2592
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Peruzzi, S., Boulanger, P.: ANKERSYN – A new gen-
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effect of antioxidants on the oxidation behaviour
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two types of material displayed dissimilar lieri, A.L., Martinez, A.G.T.: Mechanical behaviour
C., Granda, M.: Oxidation behaviour of magnesia–
tensile and compressive loading, which can carbon materials prepared with petroleum pitch as of MgO–C refractory bricks evaluated by stress–
be explained using finite element method binder. J. Analyt. and Appl. Pyrolysis 88 (2010) strain curves. Ceram. Inter. 38 (2012) 4035–4047
207–212 [21] Zhu, T., Lin, Y., Luo, M., Sang, S., Wang, Q., Zhao,
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[7] Sani, M.A.F., Yamaguchi, A.: Oxidation kinetics of
fractory material was found to decrease MgO–C refractory bricks. Ceram. Inter. 28 (2002) properties of MgO–C refractories containing
by 10 % due to carbon oxidation between 835–839 graphite oxide nanosheets (GONs). Ceram. Inter.
39 (2013) 3017–3025

Received: 24.03.2014

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