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Process metallurgy

Dedicated toProfessor Dr.-Ing. haM Dr. h. c. Dieter Janke on the occasion ofhis 65th birthday

Viscosity of slags
Dirk Mudersbach, Peter M. Drissen, Michael Kuhn, and Jurgen Geiseler

The experimental determination of the viscosity of slags proves to be difficult. Therefore models for calculation have been developed. The
Urbain-Ill-model is very often used for slags. In order to further improve its accuracy, the Forschungsgemeinschaft EisenhOttenschlacken
(FEhS) modified this model by adjusting the coefficients of Weymann's temperature relation in dependence of the CaO/Si02-basicity of
the slag: '7 = A- Texp(10 3-817) with A = f (CIS-basicity); B = f (Xoxides). Viscosities calculated by means of this modified model fit well with
measured values. It has been shown that the application of this model enables the optimisation of metallurgical reactions and processes.
Furthermore it should be possible to optimise those properties of the solidified slag which are influenced by the viscosity of the liquid slag.
Thus the production of construction materials could be further improved to fulfil the highest quality requirements.

Viskositiit von Schlacken. Die experimentelle Bestimmung der Vlskositat von Schlacken erweist sich als schwierig. Von den daher
entwickelten Rechenmodellen wird das Urban-Ill-Modell haufiq fur Schlacken angewandt. Urn dessen Genauigkeit weiter zu verbessern,
modifizierte die Forschungsgemeinschaft EisenhOttenschlacken (FEhS) dieses Modell, indem sie die Koeffizienten der Weymann'schen
Temperaturbeziehung in Abhanqlqkslt von der CaO/Si02-Basizitat definiert: '7 = A Texp(1 0 3 -817) mit A = f (CIS-Basizitat); B = f (XOxide).
Die Viskosltaten, die mit diesem modifizierten Modell errechnet werden, stimmen gut mit den gemessenen Werten Oberein. Es wird ge-
zeigt, daB die Anwendung dieses Modells die Optimierung metallurgischer Reaktionen und Prozesse erm6glicht. DarOber hinaus solite es
m6glich sein, diejenigen Eigenschaften der erstarrten Schlacke zu optimieren, die durch die Viskositat der flOssigen Schlacke beeinfluBt
werden. Auf diese Weise k6nnte die Herstellung von Baustoffen aus EisenhOttenschlacken weiter verbessert werden, urn h6chste Quali-
tatsanspruchs zu erfOlien.

The viscosity of slags which is the ability of one layer of It is widely accepted that slags follow Newton's relation-
molecules to move over an adjacent layer of molecules is ship (1) and that the viscosity is a function of composition
of great importance for metallurgical reactions and for the and temperature. The temperature dependence is expressed
performance of metallurgical processes [1...3]. The trans- by the Arrhenius relationship:
port of mass and heat, the solubility of slag formers and
additions, the separation of metal and slag are improved by 1'/ = 1'/0 exp(EIRT) (3)
low viscosities. But on the other hand a low viscosity of
aggressive slags increases the corrosion of the refractory where R is the gas constant, E the activation energy and T
materials of metallurgical vessels. the temperature expressed in K.
These are only few examples why metallurgists for op- Viscosity today is expressed in the S.L-unit Pa-s = N·
erational reasons are interested in the viscosity of slags. It s/m-', whereas in the past it was given in the CGS-unit
is well known that the viscosity is mainly influenced by Poise [Pl. Both are related by equation:
the chemical composition and temperature of a slag [I; 2;
4]. But even in the late 1960s it has been stated that only 0.1 Pa-s = 1 P. (4)
few experiences exist on viscosity because it is rather dif-
ficult to measure the viscosity of slags [5].
Common methods to determine the viscosity of
Theoretical considerations slags

The viscosity (11) is the correlation factor between shear A lot of established and proposed methods exist to de-
termine the viscosity [6...23]. Most of them have been
stress (r) and the gradient of velocity (y) as it has been
summarised in literature [1; 2].
defined by Newton 300 years ago:
Most frequently used is the method of rotation of con-
(1)
centric cylinders, which has been used for measuring the
T=1'/'Y'
viscosity from 0.01 to 1000 Pa-s [14; 24] and which is
Liquids which obey equation (1) are called Newtonian used for the investigations reported below [25].
liquids. But if a distinct shear stress To is necessary to start A cylindrical body is immersed into a crucible which
viscous flow the equation will be changed to: contains liquid slag. The viscosity can be calculated using
equation:
T=To+1'/·Y· (2)
(5)
Dipl.-Ing. Dirk Mudersbach; Dr.-Ing. Peter M. Drissen; Dr.-Ing. Mi-
chae/ Kuhn: Professor Dr-Ing. Juergen Geise/er, Research Association
with Md - torque necessary to generate n revolutions of the
for Iron and Steel Slags (FEhS), Duisburg, Germany. cylindrical body with the dimensions h (height) and Rb

86 steel research 72 (2001) NO.3


Process metalfurgy

-
mechanical problems, like tumbling of the body. The up-
f
per limit is given by the liquidus temperature TJi q of these
= slags.
- Basically, viscosity should only be determined within
'r--. that range of temperatures which guarantees a homogene-
e
9 ous liquid. At Tliq crystallisation starts and the slag be-
d comes a heterogeneous mixture of liquid and crystals. This
leads to a sudden increase in viscosity with falling tem-
perature. Viscosity data of this temperature range are no
~ 1 longer reliable. Crystals tend to grow on the surface of the
\ 1/ a cylindrical body as it is the coldest part in the system and
lead to incorrect results.
To minimise temperature gradients the crucible has to be
placed close to the centre of the Tammann furnace. Hence
a long distance between the rotating body and the torque
measuring device is necessary. This involves further me-
chanical problems. The concentric position of body and
b
c crucible and the immersion depth of the body in the slag is
difficult to control. Furthermore a high stiffness of the
shaft is required and any bending has to be prevented.

Mathematical models for calculating the viscosity


/ \ of multicomponent slags

From these considerations it is obvious that the experi-


mental determination of viscosities is difficult. Conse-
quently mathematical models have been developed to
calculate slag viscosities [26...29]. These models are based
9 on measured viscosities of slags of binary and ternary
systems. The data calculated by these models can be con-
sidered as an approach which has to be improved by fur-
ther measurements but usually they permit a prediction of
the viscosity of slags depending from their composition
and temperature.
Compared to other proposals the models developed by
9 Riboud [26] and Urbain [27...29] until now have lead to
Figure 1. Device for measuring the viscosity of slags, based on
the rotation of concentric cylinders [25]
the most reliable data [2]. But there are yet some insuffi-
cient results which caused further modifications. There-
fore, FEhS has made attempts to modify the existing mod-
(radius). R c is the radius of the crucible. Md represents the els of Riboud and Urbain [30].
shear stress and n the velocity gradient of Newton's rela- The model of Riboud has been developed to determine
tionship (1). This formula is valid only if h> Rb and R«. the viscosity of casting fluxes [31]. Using some adaptions
A typical arrangement is shown in figure 1. A crucible this model can be used for calculating the viscosity of
(b) and cylindrical body (c) are placed into a Tammann slags containing higher amounts of alkalis and fluorspar.
furnace (a). The height within the furnace has to be ad- The original model of Urbain served for the calculation
justed to meet the range of constant temperature. The shaft of viscosities of silicate and alumina silicate melts of sim-
of the rotating body is connected by a flexible coupling (d) ple chemical composition. The model is used in ceramic
to the torque of the measuring device (e) and a motor drive processes to determine the melting behaviour. The Urbain-
(f). The whole system is placed on crossed sliding car- III-model has been modified by FEhS to improve the accu-
riages (not shown) to centre the cylindrical body in the racy of the calculation for blast-furnace- and steel slags by
crucible. Temperature control is performed by several means of an adjusted Weymann's temperature relation:
thermo-couples (g).
This device has been used for viscosity measurements of -In A = m-B + n (6)
slags belonging to the system CaO-MgO-Si02-Fe203 [25].
The typical range of viscosities has been 0.15 to about 0.8 with B = f (Xglass formers, xamphoteries, Xmodifiers) and x =
Pa·s. The lower limit is given by the dimensions of cruci- mole fraction of the different components:
ble and body. In fact it is a compromise aiming at low - glass formers: Si4+, p5+,
viscosity data (Rb "" Rc) according to equation (5) and - amphoteries: AI3+, B3+, (Fe3+),

steel research 72 (2001) NO.3 87


Process metallurgy

1,5
slag A: 50.0CaO~50.0SiC)"
furnace slags within the range of homogeneous melt (in
slag B: 35.0CaO~50.0SiOr15.0Fe2OJ this case> 1350 Qq. Figure 3 shows that again the calcu-
slog C: 22.9Co040.5SIO,.20.4MgO·16.2Fe,O,
me: measured (25] lated and measured viscosities are in good agreement.
cc: calculated With FEhS·model
a: Fe20:! as amphoterles It has been proposed to estimate the melting temperature
m: F 0 as modtner
from the increase in the slope of the curves 1] = fCT).
Though this only allows a rough estimation sometimes it
may be helpful to estimate the melting range in this way.
In figure 4 the measured melting points fit well with that
temperature at which the curves tend to the vertical [4].
A-cc.

-...
A-ms. Application of the FEhS-model
0,0 +.~._--_.~_ ~_ .. .. ~.~.-"- "~- ..,, .. ..,, .
~._

1350 1400 1450 1500 1550 1600 1650 1700


In the following three examples for the application of the
temperature, °c
FEhS-model are reported.
Figure 2. Measured [25] and calculated viscosities of three syn-
The first example relates to the treatment of liquid LD-
thetic slags
slag with oxygen and sand [32; 33]. The addition of sand
leads to an increase in viscosity. Therefore by calculating
- modifiers: Ca 2+, M g2+, Fe 2+, (Fe 3+), Na+, K+, Mn 2+, the viscosity it could be shown that this treatment has to be
Cr 3+, Ti 4 +, . started with oxygen blowing to oxidise iron and FeO. The
The parameters A and B are expressed in molar quanti- addition of sand will be started as soon as a distinct vis-
ties. A is a function of m, E w , v and f..Sy . B is a function of cosity of the slag is given.
Ew and My. My and f..Sy are the partial molar enthalpy A similar problem arose when it had been investigated to
and entropy, respectively. m and v are mass and volume of modify the composition of LD-slag by reduction of
the structural unit, E w the energy of the well [27]. FeO/Fe203 and by charging additions in order to approach
While the coefficients m and n of the Urbain model are the composition of portland cement clinker [34]. Both the
constant, FEhS adjusted these coefficients to the reduction of FeO/Fe203 and the additions cause an in-
CaO/Si02-basicity. For 54 oxide-silicate and alumina- crease in viscosity and melting temperature, figure 5. In
silicate melts the parameters A and B of Weymann's equa- order to not impede the reactions the viscosity has to be
tion (6) have been determined experimentally. kept low. By means of the model the possible amount and
The viscosity can be calculated according to equation (7): the right moment of charging additions to change the com-
position and charging fluxes to decrease the viscosity has
1] = A ·T·exp(l03.B!l). (7) been calculated.
The viscosity at all temperatures has been increased by
Results obtained by using the FEhS-model have been partial reduction to Fe203 mass contents of 7 % and yet
compared first with the measured viscosities of synthetic more by meeting a composition which is similar to a
slags of the system CaO-MgO-Si02-Fe203 [25]. Fe203 clinker composition. By continuous calculations it was
may be considered both as modifier and as amphoteric possible to adjust the slag's composition to keep the vis-
oxide. It has been derived from the comparison of results cosity sufficiently low by means of additions of alumina
that the calculated data fit best if Fe203 is considered as and/or fluorspar. These calculations make it possible to
modifier, figure 2, which is in a agreement with the inter- arrive at the intended composition but preventing slag
pretation of most researchers before. compositions with higher viscosity and worse reactivity.
Subsequently an additional comparison has been per- Thus an optimisation of the slag path - which is the graphi-
formed using a lot of operational multicomponent blast- cal description of concentrations during a metallurgical

ICaOISI02-baslclty = 1,1 ; MgO = 13 % ; A~o, = 8 % 3.5 -.. ,......----+------r------------,


3,0 Imonlng point In 'C I
2,0 ...-------,------.,------,---.....,.-""?"'-----=-:-,
temp. exp calc.
2,5
1300"C 2.01 1,42
1,5 1350"C
1400"C
0.99
0.63
1,01
0,73
e
n. 2,0
.
''"
Q.
1450"C
1500"C
0.50
0.40
0.55
0,42 f:Il,.5 t .J
basicity = CoOISlo, l.
~1,0 ·· : '""""--(,'--.;,:,'......
1550'C 0.31 0,32
'"
0
c 1600"C 0.25 0,25 '>
~ 1650'C 0,20 0.20 1.0
1700'C 0,15 0.15
0,5
0.5

0,0 +-----;.----i---..;.----i----i---..;.----i--~ 0,0 L-~-~--~-~-~--===:t:=::::t


1300 1350 1400 1450 1500 1550 1600 1650 1700 1300 1325 1350 1375 1400 1425 1450 1475 1500
temperature, °c temperature, °C

Figure 3. Measured and calculated viscosities of an operational Figure 4. Viscosity and melting point of blast-furnace slags with
blast-furnace slag figures in % refer to mass contents) different basicities [4]

88 steel research 72 (2001) NO.3


Process metallurgy

0.7 r-r---,----.--,---,----,---,---,--,---,--,
porosity and strength of the solid slag additionally are
0.6 influenced by further parameters. But it should be possible
to aim at distinct limits of viscosity which lead to suffi-
0.5
ciently low porosity and high strength of air cooled and
processed slags.

Conclusion

0.1 Metallurgical reactions and processes are to a large ex-


tent influenced by the viscosity of slags. But it is rather
1250 1300 1360 1400 1450 1500 1660 1600 1650 1700 1750 1800 difficult to determine the viscosity experimentally. There-
temperature, QC fore mathematical models like the Urbain-III-model have
Figure 5. Viscosity of clinker and steel slags, original and modified been developed, which proved to allow the calculation of
(figures in % refer to mass contents) slag viscosities.
Due to some insufficient results the Urbain-Ill-model
process in the respective slag system - will be possible by has been modified by FEhS. Using this modified model a
aiming at low viscosities. good correlation with measured viscosities could be dem-
By another example it has been investigated, whether the onstrated. Furthermore this modified model has been used
optimisation of the viscosity could also influence proper- to develop a slag path during a metallurgical process or
ties of the solidified slag. These investigations have been treatment with sufficiently low viscosities and good reac-
performed using blast-furnace slags. It is well known that tivities.
air cooled blast-furnace slag is more or less porous [35]. Furthermore, it should be possible to optimise those
The porosity results from the release of solved gases like properties of the solidified slag which are influenced by
N2, H2, CO etc. which cannot escape from the solidifying the viscosity of the liquid slag as could be stated by pre-
slag. Besides other influences a low viscosity will facilitate liminary investigations. Therefore, viscosity calculation
the removal of gases. may be a good support to aim at slags with optimal prop-
For a great number of blast-furnace slags the relationship erties.
of viscosity and porosity has been investigated. The (A 01 631; received: 21. December 2000)
chemical composition of operational slags has been opti-
mised by means of the FEhS-model to guarantee a suffi- References
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[in:] Schlacken in der Metallurgic, Verlag Stahleisen GmbH,
for 1500 DC, a CaO/Si02-basicity of 1.05 and varying
Dusseldorf 1984.
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Iaitiers du haut foumeau, Rap. C.N.R.M., April 1964.
cosity probably will make it feasible to produce solid slags
[5] Langhammer, H-1.; Geck, H-C.: Arch. Eisenhuttenwes, 38 (1967)
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It is obvious that a strong correlation cannot exist because [8] Krabiell, H1.: stahl u. eisen 64 (1944), p. 399.
[9] Mackenzie, 1.D.: Trans. Rarad. Soc. 52 (1956), p. 1564.
[I 0] Endell, K; Heitkamp, C.; Hax, L.: Arch. Eisenhuttenwes, 10

I CaO/SI0 2-baslclty = 1,05 1


(1936), p. 85.
[I I] Heutkamp, C.; Endell, K: Glastech. Ber. 14 (1936), p. 89.
[I 2] Machin, 1.5.: Amer. Ceram. Soc. 28 (1945). p. 310.
[I 3] Bockries, 1.O'M; Mackenzie, 1.0.; Kitchner, 1.A.: Trans. Farad.
Soc. 51 (1955), p. 1734.
[14]Bockries, 1.O'M; Lowe, D.C: Proc. Royal Soc. A 226 (1954). p.
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[15] Van der Coif 1.; Howat, D.D.: J. South African Inst. Min. & Met-
allurgy 79 (1979), p. 255.
[I 6] Dietzel. A.; Bruckner, R.: Glastechn, Ber. 28 (1955), p. 455.
[17] Frohberg, M C.; Weber, R.: Arch. Eisenhiittenwes. 36 (1965), p. 477.
[18]Handfield, C.; Charette. C. C.: Canad. Metallurg. Quart. 10 (1971),
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[I 9] Hofmann. s.e.. stahl u. eisen 79 (1959), p. 846.
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AIME, 1961, p. 97.
[2 I] Pohlmann, H-J.: Glastech. Ber. 49 (1976), p. 177.
[22] Schenck, H; Frohberg, MC. : Arch. Eisenhuttenwes, 32 (1961), p.
Figure 6. Viscosity of blast-furnace slags at 1500°C 521.

steel research 72 (2001) NO.3 89


Process metallurgy

[23] Schenck, H; Frohberg, MG.: Arch. Eisenhiittenwes. 33 (1962), p. [31] Viswanathan, NN; etal.: steel res. 70 (1992), p. 2.
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(1978), p. 264. and Steel Slags-Properties and Utilisation, Schriftenreihe der FEhS,
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Properties and Utilisation, Schriftenreihe der FEhS, Heft 8, p. 213. tung, ECSC R. & D.- project EUR 16623 DE.

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