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Review PaPeRs
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
Review PaPeRs
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
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
Review PaPeRs
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
Review PaPeRs
Review PaPeRs
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
Review PaPeRs
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
Review PaPeRs
Review PaPeRs
Review PaPeRs
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
er along with monticellite solid state solu- and because of in-situ formation of desir- [14] Aneziris, C.G., Hubalkova, J., Barabas, R.: Micro-
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-
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tivated carbon. Advanced ceramics. 15.01, pp.19 (2001) 1037–1047
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(2003)
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[3] Figueiredo Jr, A., Bellandi, N., Vanola, A., Zamboni, 2393–2405
washing out of carbon, even though slight [17] de la Torre, A.G., Valle, F.J., De Aza, A.H.: Direct
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-
tensile strength for both pitch-bonded and eration of carbon-bonded magnesia carbon bricks. iour of magnesia carbon refractories. J. Eur. Ceram.
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[5] Gokce, A.S., Gurcan, C., Ozgen, S., Aydin, S.: The [19] Baudson, H., Debucquoy, F., Huger, M., Gaulta C.,
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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–
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39 (2013) 3017–3025
Received: 24.03.2014