Refractories and Industrial Ceramics Vol. 46, No.

4, 2005

UDC 666.762.3.017:620.178.16

ATTACK OF MOLTEN SLAG ON REFRACTORY

S. A. Suvorov1 and P. V. Plyukhin1

Translated from Novye Ogneupory, No. 6, pp. 86 89, June, 2005.

The effect of magnesium oxide on the phase composition of metallurgical slag is studied. Heterogeneity of the
slag and its final melting point are shown to increase with MgO concentration. A model for the slag infiltration
into a periclase refractory is considered. A nomogram is plotted to show the dependence of the depth of slag pene-
tration on slag viscosity, contact angle, surface tension, pore radius, and molten slag - refractory contact time.

Modern steelmaking technology places the ever-de- and phosphoric (PO4)3. These ions are capable of combining
manding requirements on the performance of the refractory to form associates of different kind. Modern concepts of the
lining. The cost of the refractory lining (installation, mainte- structure of the liquid slag are largely based on an analogy
nance, repair, etc.) accounts for a considerable portion of the
total product cost; therefore reduction of the refractory cost TABLE 1. Major Minerals of the Quaternary System
and extending the service life of the refractory lining provide CMAS
a route towards improving the efficiency of steelmaking pro- Melting
cesses. Mineral Mineral
Chemical formula (decomposi-
label name
The high-temperature damage to the working layer of the tion) point, C
refractory lining is caused by the attack of molten slag and CaO Al2O3 2SiO2 CAS2 Anorthite 1590
hot gases, by the displacement of liquid and solid media, and
by mechanical and thermomechanical stresses. Recently, sec- a-CaO SiO2 CS Wollastonite 1544
ondary metal processing methods have been gaining an 2CaO Al2O3 SiO2 C2AS Gehlenite 1590
ever-increasing acceptance that providing thereby routes to- CaO MgO 2SiO2 CMS2 Diopside 1391
ward improving the metal quality. For this reason, the need
MgO SiO2 MS Clinoenstatite 1557
arose for new refractory materials that would minimize the
steel contamination, improve performance and physico- 2MgO 2Al2O3 5SiO2 M2A2S5 Cordierite 1470
mechanical properties of the refractory lining and extend its SiO2 Cristobalite 1470
service life [1]. Listed in Table 1 are minerals that make part 2CaO SiO2 C2S Larnite 2130
of the slag of a quaternary system CaO MgO Al 2O3 SiO2
2CaO MgO 2SiO2
[2]. All the minerals in Table 1, except for melilite (a solid so-
+ 2CaO Al2O3 SiO2 Melilite 1390
lution of kermanite and gehlenite), have a crystal structure.
The composition and melting points of actual metallurgi- 3CaO MgO 2SiO2 C3MS2 Merwinite 1598
cal slags (each a combination of materials presented in Ta- CaO MgO SiO2 CMS Monticellite 1300
ble 1) are given in Table 2. 2CaO MgO 2SiO2 C2MS2 kermanite 1458
According to the widely recognized ionic theory [2],
MgO Periclase 2800
molten slags may contain: (i) metal cations (Ca2+, Fe2+,
Mg2+, Mn2+, and Al3+); (ii) simple anions (O2 and S2); (iii) a-CaO SiO2 CS Pseudowollastonite 1540
complex ions silicon-oxygen [(SixOy)z, where x, y, and z 3CaO 2SiO2 C3S2 Rankinite 1450
are positive integer, aluminum-oxygen [(Al2O3)3, (AlO4)5], Al2O3 SiO2 AS Sillamanite 1545
SiO2 Tridymite 1728
1 2MgO SiO2 M2S Forsterite 1890
St. Petersburg Technological Institute (Technical University),
St. Petersburg; Gruppa Magnezit Joint-Stock Co., Russia. MgO Al2O3 MA Spinel 2135

253
1083-4877/05/4604-0253 2005 Springer Science+Business Media, Inc.
254 S. A. Suvorov and P. V. Plyukhin

Fig. 1. Nomogram showing the dependence of the depth of penetration on viscosity, surface tenaion, pore radius, contact angle, and contact
time: a) q = 20, q = 15, q = 10; b) t = 1 min; t = 60 min; t = 120 min.

between the structure of crystalline and molten silicates. On ture, pore size, viscosity, surface tension, slag composition,
heating, the slag undergoes change associated with the for- gas medium, hydrostatic pressure in the melt, and the depth
mation of chemical compounds, melting, and polymorphic of penetration. The infiltration of metal and slag into the
transformations. The slags were examined by differential pores increases the wear rate of the refractory material; a
thermal analysis using a VTA-981 high-temperature thermo- so-called capillary impregnation takes place, which is also
analyzer. controlled by the wettability of the refractory material with
The slag bulk during crystallization is most likely repre- slag. The pore size is likewise a factor capable of affecting
sented by melilite, pseudowollastonite, and rankinite. Spinel, the physicochemical properties of refractories to a significant
larnite, monticellite, forsterite, anorthite, diposide, tridymite, extent: porosity play a pivotal role in the wear of refractories
etc. occur in much smaller amounts. FeO, owing to its rather because of the slag erosion. The penetration of a slag into a
high slag percentage, is capable of forming ferruginous refractory can be characterized by the equation [3]
akermanite 2CaO FeO 2SiO2 with a melting point of
965C that makes part of melilite. Manganese is likewise a cos( q / 180p )
x (k, q, h): = k; (1)
component of melilite. When present in larger amounts (for 2.86 14. h
example, in the processing of ferromanganese), it may take
part in the formation of manganosite MnO and manganous k (r, s, t): = rst , (2)
monticellite. Iron and manganese oxides are also found as
components of melilite Ca[(Mn,Fe,Mg,Al)(Si,Al)2O7]. where x is the depth of penetration of the melt, cm; s is the
The effect of MgO on the phase composition of metallur- surface tension at the melt gas interface, mJ/m2(egr/cm2);
gical slag was studied. The heterogeneity of slag was shown q is the contact angle, deg; r is the pore radius, cm; h is the
to increase with magnesium oxide content. melt viscosity, Pa sec; t is the refractory-and-melt contact
Factors that control the penetration of liquid metal and time, min; 2.86 is a factor to take account of the capillary ra-
molten slag into pores of a refractory material are: tempera- dius ratio for the large and narrow parts of a capillary; 1.4 is
the tortuosity factor (in materials of granular com-
TABLE 2. Composition and Melting Points of Metallurgical; Slags position, it typically lies within 1.2 1.6).
Chemical composition, wt.% Slag temperature, C Equation (1) was used to calculate the depth of
Slag penetration under the following conditions [2, 4, 5]:
No. SiO2 Al2O3 FeO incipient final
CaO MnO MgO
melting point melting point slag viscosity, 0.05 0.2 Pa sec; contact angle,
1 51.4 12.8 23.3 1.7 1.7 1105 1930 10 20; surface tension, 400 450 mJ/m 2; pore
2 43.7 15.8 7.6 17.1 5.5 7.6 1085 1780 radius, 5 50 mm, and contact time, 1 120 min.
Nomograms showing the dependence of the
3 4555 1220 7 25 2.5 3 6 12 1100 >1750
depth of impregnation on the aforementioned fac-
4 40.8 15.1 10.7 16.7 6.9 7.7 1080 >1725
tors calculated by Eq. (1) are presented in Fig. 1.
Attack of Molten Slag on Refractory
Degradation of the working layer is associated with the
transformation of phase and chemical compositions along
the temperature gradient involving the slag and metal infil-
tration and the loss of weight; in other words, the directional
mass transfer from the working layer to the melt because of
the dissolution and spalling of the refractory material and ex-
cessive thermomechanical stresses [1, 4, 6, 7].
The destructive attack of slag on the lining is controlled
by the concentration of MgO in the molten slag and by the
mass of slag. The amount of magnesium oxide removed from
the lining to the slag melt is determined by the mass transfer
coefficient b which is defined in terms of the Danckwert
model [7] as
b = (D/t)1/2, (3)
where D is the molecular diffusion for magnesium oxide.
The specific mass transfer rate i is
i = b Dc , (4)
where Dc = C* C; C* is the saturation concentration and C
is the actual concentration of the refractory oxide in slag.
Hence the wear rate of the lining is
d = tDc( D / t)
1/ 2
, (5)
cf
255
where cf is the concentration of the refractory oxide dis-
solved in slag.
The rate of dissolution for the periclase refractory was
found to be 2.9 4.3 mm/min.
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