Overview Slag Properties
Predicting Slag Viscosities in
Metallurgical Systems
A. Kondratiev, E. Jak, and P.C. Hayes
Slag viscosity is a major process
variable for most pyrometallurgical
smelting and refining process opera-
tions. While extensive measurements
have been made of slag viscosities, it is
not practicable to provide data on all the
possible combinations of compositions
and process conditions encountered
in metallurgical practice. This article
reviews the mathematical models that
have been developed to predict slag
viscosities and provides some advice
on the factors to be considered in their
selection and use.
INTRODUCTION
The flow behavior of slags is an
important factor in many metallurgical
systems, influencing, for example, the
ability to tap the slag from the reactor,
the efficiency of separation of slag
from metal and matte phases, the extent
of slag foaming, the performance of
continuous-casting fluxes, and the
kinetics of metal smelting and refining
reactions. A common type of fluid flow
encountered in industrial applications
is a shear flow. The behavior of a fluid
material subjected to shear stress can be
characterized by the shear viscosity, η
(kg m–1 s–1 or Pa s), which for Newtonian
behavior is independent of shear rate,
and is called the dynamic viscosity
coefficient.1–3 In the context of the
current review, the term viscosity is used
to describe dynamic viscosity.
The ranges of viscosities that are
typically encountered in metallurgical
systems include 10–3–10–2 Pa s (1 Pa s
= 10 poise) for liquid metals, molten
salts, and mattes, and 10–2–1010 Pa s for
slags.4–8 In practical terms, it becomes
difficult to tap free-flowing fluids with
viscosities greater than 15–25 Pa s;9
these values then represent the upper
limit of interest for most slag systems.
The phase equilibria and the viscosity
behavior of the slags are determined
2002 November • JOM
by key process parameters, including
the bulk composition of the slag, the
effective oxygen partial pressure in the
slag phase, and the temperature.
In slag systems, the chemical char-
acteristics, such as bonding and short-
range order within the melts, have a
major influence on viscosity. Chemical
components such as SiO2, P2O5, and
B2O3 possess strong, highly covalent
metal-oxygen bonds, leading to high
liquid viscosities. Alkali and alkali earth
In slag systems,
the chemical
characteristics, such
as bonding and
short-range order
within the melts, have
a major influence
on viscosity.
oxides, in contrast, exhibit highly ionic
behavior and form low-viscosity melts.
The addition of alkali, alkali earth, and
transition metals to silicate melts has the
effect of changing the type and number
of the metal-oxygen nearest neighbors
and of lowering the fluid viscosities; the
magnitude of these effects are strongly
dependent on the components and their
proportions present in the melt. The
transition metals exist in different
oxidation states (e.g., iron can be
present as Fe2+ or Fe3+) and, since
they have different influences on the
physicochemical and thermodynamic
properties of the system, are considered
as separate components in the system
(e.g., FeO and Fe2O3).
A number of compilations and
reviews are available that summarize
and evaluate the experimental data
on slag viscosities published in the
literature.5,7,8,10–13 It is often the case,
however, that experimental information
on the slag viscosities is not available
for the particular composition and
conditions of interest to a particular
practice. In this event, mathematical
models can be used to predict the trends
in viscosity as a function of the key
variables, and so assist in the selection of
process conditions and the optimization
of the performance of the system of
interest.
SINGLE-PHASE SLAG
SYSTEMS
The viscosities of fully liquid slags
have been found to exhibit Newtonian
behavior at the low shear strain rates
that are commonly encountered in
metallurgical practice.
A variety of approaches and math-
ematical formalisms have been used to
describe the viscosities of liquid slags
as a function of temperature and of
composition. Comparisons between
the various model predictions and
experimental data are commonly quoted
in the literature, and in some cases a
number of models have been compared
and evaluated to assess their usefulness
for applications in particular composition
ranges.11,14 A summary covering most of
the published viscosity models suitable
for use in metallurgical applications and
the particular chemical and metallurgical
systems to which they have been applied
is given in Table I. The various models
have been listed in groups selected on the
basis of similarities in the temperature
and composition dependences used in
different viscosity models. The classifi-
cation by temperature includes empiri-
cal, Arrhenius, Weymann-Frenkel,
41
 Table I. Classification of Slag Viscosity Models

Model Type

Temperature Composition Name Chemical Systems Comments/Validity

Empirical Empirical Sage-McIlroy15 Coal ash slags Valid only for limited
Utigard-Warczok16 “Fayalite-type” slags composition-temperature
Watt-Fereday17 Coal ash slags ranges
Gupta18 Industrial mold fluxes
Saxen19 Iron blast furnace slags
Empirical Empirical: Linear Bottinga-Weill20 Binary and ternary alkali Validity reported for
(major components) and alkali earth-SiO2 systems 1,200–1,800°C and
35–81 mol% SiO2 with
470 coefficients

Arrhenius Empirical Shaw21 Binary and ternary alkali

and alkali earth-SiO2 systems
Arrhenius Empirical S2 22 Na2O-K2O-CaO-MgO-FeO- Valid only for limited
Al2O3-SiO2 composition-temperature ranges
Arrhenius Optical basicity NPL23 Wide range of industrial Optimized using a limited set
slags and mold fluxes of experimental data; Requires
(Na2O-K2O-CaO-MgO-FeO-MnO- use of optical basicity data
CaF2-Fe2O3-TiO2-Al2O3-SiO2)

Weymann-Frenkel Urbain Urbain24,25 (Mg, Ca, Mn)O-Al2O3-SiO2 Different sets of coefficients

and corresponding binaries + for each ternary system
(Ba, Pb, Fe, Sr)O-SiO2
Weymann-Frenkel Urbain Riboud26 Industrial mold fluxes Valid only for limited
(Na2O-CaO-CaF2-Al2O3-SiO2) composition-temperature ranges
Weymann-Frenkel Urbain Senior-Srimivasachar27 Coal ash slags (Na2O-K2O- Optimized on large
CaO-MgO-FeO-Fe2O3- set of data, but not
Al2O3-TiO2-SiO2) valid for whole range
of compositions
Weymann-Frenkel Urbain Streeter28 Particular set of coal ash Valid only for limited
(+ correction slags (Na2O-K2O-CaO-MgO- composition-temperature ranges
factor) FeO-TiO2-Al2O3-SiO2-SO3)
Weymann-Frenkel Urbain (modified) Kondratiev-Jak12,13 CaO-FeO-Al2O3-SiO2 Valid for whole composition
at metallic iron saturation range within four-component
system

Weymann-Frenkel Quasi-structural: Zhang-Jahanshahi29,30 CaO-MgO-MnO-FeO-Fe2O3- Requires use of TD cell

Cell model
Bockris-Reddy Quasi-structural:
Atomic pair model
Quasi-structural: network parameter + basicity index
Al2O3-SiO2 model parameters
Reddy31 (Ca, Mg, Ba, Sr)O-SiO2 + Yokokawa TD atomic
(Na, K)2O-B2O3, Na2O-B2O3-SiO2 pair model required to
calculate the concentrations
of bridging O
Iida32 Mold fluxes and Requires use of basicity index
metallurgical slags

Eyring TD: Gibbs free energy KTH33,34 Metallurgical slags Coefficients are not published
of mixing
TD: Adam- TD: Configurational Configurational General model for silicate Configurational entropy of
Gibbs theory entropy entropy35,36 systems slag required
TD: Clausius- Empirical McCauley- Industrial slags (Na2O-K2O-- Valid only for limited
Clapeyron Apelian37 CaO-MgO-FeO-MnO-ZrO2- composition-temperature ranges
CaF2-Al2O3-B2O3-SiO2)

Eyring, Bockris-Reddy, quasi-structural,
and thermodynamic (TD) models. The
compositional classification includes
empirical, optical basicity, Urbain,
quasi-structural, and TD models.
Fully empirical models16–20 simply
represent convenient mathematical
descriptions of slag viscosity as a func-
tion of temperature and bulk composi-
tion; there is usually no fundamental
linkage between the mathematical
formalism and the physicochemical
behavior. The Bottinga and Weill20
model has been developed for a wide
range of silicate systems of geological
interest. The authors used a linear
dependence of viscosity on composition,
and different coefficients are provided
for each temperature range. This model
differs from most empirical models in
that there is an attempt to take into
account aspects of the chemistry. To do
this, structural complexes (associates)
were introduced into the model as major
components to take into account a dual
behavior of aluminum oxide in the
(alkali, alkali earth) metal oxide-silica
systems. The Bottinga and Weill model
has been validated against experimental
viscosity data for a wide range of tem-
peratures and compositions, however,
it does require a large number (470) of
coefficients to do this. Most empirical

42 JOM • November 2002

viscosity models cannot be recom-
mended for use for compositions and
temperatures even slightly different
than those reported by the authors;
to do so may lead to quite erroneous
results.
A number of viscosity models make
use of the well-known Arrhenius
equation38 to describe the temperature
dependence of silicate viscosity. How-
ever, the compositional dependencies
of the models are still fully empiri-
cal.21,22 Shaw21 introduced Arrhenius
temperature behavior into the Bottinga-
Weill model and incorporated the
influence of H2O content in the melt
on its viscosity, which is important for
geological systems.
More advanced viscosity models
introduce a more fundamental physi-
cochemical basis into the viscosity
description. For example, the NPL
model developed by Mills and Sridhar23
also uses the Arrhenius equation
for temperature dependence of slag
viscosity, but links the compositional
dependence to the corrected optical
basicity of the slag, which in turn can
be obtained from experimental data or
estimated.23 This model was successfully
applied to a range of metallurgical slag
compositions as well as mold fluxes,
although it can be used only in limited
compositional ranges.
Many viscosity models are based on
the Weymann-Frenkel (WF)39,40 kinetic
theory of liquids. In many cases, these
models have been found to give better
agreement with experimental data
than can be achieved using the Arrhe-
nius expression. The modified WF
equation for slag viscosity developed by
Urbain24,25 is given by the expression:
η = A T exp (103 B/T) (1)
where A and B are compositionally
dependent parameters. Three classes
of oxides are introduced in the Urbain
model: glass formers, modifiers, and
amphoterics. Silicon dioxide (SiO2) is an
example of a glass-forming component,
which is characterized by strong bonds
and very high viscosity. Modifier oxides
containing e.g., Na+, K+, Ca2+, Fe2+,
and Mg2+ ions modify or break strong
internal bonds and lower the viscosity.
Oxides such as Al2O3 or Cr2O3 can
behave either as modifier or glass
former, depending on the concentrations
2002 November • JOM
of other constituents of slag. From the
analysis of experimental data, Urbain
postulated that the parameter B increases
proportionally to the third power of XG;
(XG, XM, and XA are the corresponding
molar fractions of glass-forming, modi-
fier, and amphoteric components). At
a given XG, the parameter B has a
maximum value at the intermediate
ratio of modifier to amphoteric fraction,
XM/(XM+XA), this latter compositional
dependence can be described by the
second power parabola. The parameter
A is linked to B by the “compensation
law”: lnA = –mB + n, where m and n
are constants. Urbain applied this
model only up to three-component
systems.25 Riboud et al.,26 using Urbain
formalism with corrected compositional
dependences of A and B, successfully
applied the model to describe the
viscosities of some industrial mold
fluxes. Streeter et al.28 also used the
WF (Urbain) formalism with some
corrections introduced to describe
viscosities of their particular systems of
interest. Kondratiev and Jak12,13 further
modified the formalism developed by
Urbain in order to describe viscosities of
multi-component slags. This modified
formalism was then used to describe
the viscosity behavior of slags over
the whole composition range in the
four-component system Al2O3-CaO-
FeO-SiO2 at iron metal saturation (i.e.,
reducing conditions). This represents the
process conditions present in a number
of major industrial slags systems. Their
model uses one set of parameters and
agrees well with more than 3,000
experimental points covering four unary,
six binary, and four ternary systems,
and the liquid in the whole of the
quaternary system.
The quasi-structural models have
been developed to take into account the
complex internal structures of molten
slags. Zhang et al.29,30 developed a model
using the same WF dependence on
temperature, but linked the parameters A
and B to the concentrations of bridging,
non-bridging, and free oxygens, which
were calculated using a thermodynamic
“cell model”41 of slag structure. This
viscosity model is reported to describe
viscosities in a wide range of composi-
tions, however, information on the
parameters in the chemical thermody-
namic model is also required.42 Although
not available at present, it is expected
that the thermodynamic cell model
parameters will be published in the
literature in the near future. Hu and
Reddy31 developed their model using
the Bockris-Reddy viscosity equation,43
which is similar to the WF equation, and
the Yokokawa “atomic pair model”44 of
the slag structure. The Reddy model has
been applied to some binary systems
and some ternary borosilicates. The Iida
model32 uses a basicity index to link a
so-called structurally related “network
parameter” to the viscosity. The model
was used to describe experimental vis-
cosity measurements on mold fluxes.
Thermodynamically based viscosity
models have been developed using a
number of very different approaches.
The KTH model33,34 was developed on
the basis of the Eyring equation,45 which
is similar to the WF formalism. The
compositional dependence of the model
is expressed as a function of the Gibbs
free energy of solution. The Gibbs
free energy expression contains many
adjustable parameters, which are used
to obtain agreement with experimental
results. The model is reported to be
applicable to a wide range of systems,
from liquid metals to molten slags;
however, the required parameters
have not yet been published. The
configurational entropy model35,36 was
developed using a statistical Adam-
Gibbs theory of cooperative rearrange-
ments and links silicate melt viscosity
to the configurational entropy of the
system, which can be evaluated from
calorimetric measurements. Although
applicable to a wide range of silicates,
the major disadvantage of this model
is that it is first necessary to know or
determine the configurational entropy
of a system over a whole compositional
range in order to calculate the viscosity.
The McCauley-Appelian model37 uses
the thermodynamic Clausius-Clayperon
equation to express viscosity as a
function of temperature, but the com-
positional dependence is fully empirical.
This model can be applied only to a
limited range of compositions.
Free-volume models46–49 have been
developed and used mainly for describ-
ing viscosities of glassy systems, that
is, for viscosities higher than 1011 Pa s.
They have not, therefore, been included
in Table I.
43

MULTIPHASE SLAG
SYSTEMS
In industrial practice there are many
examples of metallurgical processes
that operate with the use of multiphase
slags containing solid-liquid or liquid-
liquid mixtures. These include systems
operating at sub-liquidus conditions
(in partially crystallized melts) or
systems where reactant materials
(e.g., concentrates or reactant carbon)
are suspended in the smelting slag.
Examples of liquid-liquid systems
include metal/slag emulsions and
slag/metal/matte mixtures produced in
liquid reaction products. In each of
these cases, the properties of the slags
can vary significantly, and control of
slag viscosity is important in the control
of the overall processes.
Both Newtonian and non-Newtonian
behavior has been observed in slag
systems. Non-Newtonian behavior is
complex and can involve pseudo-plastic
flow of the fluids. Newtonian behavior
has been reported to occur in slag
systems containing less than 10–40
vol.% solids.
There are relatively few mathemati-
cal models available to describe the
behavior of multiphase slag systems.
For Newtonian behavior, the Einstein
equation 50 predicts that, for fluids
containing a low percentage (< 5 vol%)
of fine spherical particles, the viscosity
increases linearly with the percentage of
solids. The Roscoe equation51 has also
been shown to be suitable in describing
the effect of the percentage of solids
on slag viscosity 52,53 in Newtonian
fluids.
The viscosity behavior of slags
containing a high volume percentage
of solids has been found to be more
accurately described as Bingham
plastics.53 Bingham plastics1 require
an initial shear stress (yield stress), τo,
to initiate flow; once flow occurs, the
shear stress increases linearly with the
increasing shear rate. Although there
is little experimental data on the yield
stress in slag systems, it has been
shown in metal alloy systems and other
multiphase systems that τo varies with
the relative densities of solid and liquid
phases, particle size, volume fractions of
solids, and the shapes of solids.54–57
In metallic alloy systems containing
44
dendritic crystals, it has been reported55
that the size and structure of the solid
dendrites can be modified at high shear
rates. In oxide systems, dendritic,
equiaxed, and platelike crystals are
commonly observed; the crystal shapes
depend critically on the compositions
of the crystals and the liquid phase. In
the low-shear-rate conditions present in
most metallurgical applications involv-
ing slags, shear-stress modification of
Evidence from
experimental and
modeling studies
indicate the most
important factors to be
taken into account in
estimating the
viscosities of slags
composed of solid/liquid
mixtures are the volume
percentage of solids and
the composition of the
liquid present.
the crystalline solids is not likely to be
a significant factor.
Evidence from experimental52,53 and
modeling13 studies indicate the most
important factors to be taken into
account in estimating the viscosities of
slags composed of solid/liquid mixtures
are the volume percentage of solids and
the composition of the liquid present.
In the case of solid/liquid mixtures
formed from the partial crystallization
of a slag of fixed bulk composition, the
volume percentage of each solid, the
volume percentage of liquid, and the
composition of the remaining liquid will
all vary with the process temperature;
the liquid composition in a partially
crystallized melt is not the same
as the bulk composition of the mate-
rial. Therefore, in considering the
temperature dependence of the viscosi-
ties of partially crystallized melts,
changes in both the volume percentage of
solids and the residual liquid composi-
tion have to be taken into account, since
both have significant effects on the
resulting flow properties. For example,
the cooling of siliceous smelting
slags resulting in the precipitation of
the metal-oxide spinel, M3O4 phase
containing no silica increases the silica
concentration in the residual liquid.
The resulting increase in viscosity of
the fluid stems from the increase in
viscosity of the liquid phase as a result of
compositional and temperature changes
and the increase in viscosity due to
presence of solid material.
For systems containing large particle
sizes having high-density differences
between solid and liquid phases, the
buoyancy forces acting on the particles
can become significant relative to the
viscous forces in the melt. The resultant
settling or flotation of the solid phases
will mean that segregation of the phases
within the melts can occur, and the slag
viscosity characteristics will vary with
position within the reactor. The extent
of the segregation will depend on the
bulk flow and mixing characteristics
of the reactor.58
MODELS AND TOOLS
In order to accurately predict the
viscosities of partially crystallized
melts, it is necessary to define the
phase assemblage (volume percentage
of solids, composition of solid and
liquid phases) and the effective oxygen
potential at the process temperature.
In simple binary systems, this can be
readily determined through the use of
phase diagrams.59,60 In higher-order
systems, this becomes more difficult
because of the complex chemical
changes occurring within the melts and
the limited availability of experimentally
determined phase equilibrium and
viscosity data. In these instances, it is
necessary to utilize a combination of
thermodynamic and viscosity modeling
tools.
The relative stabilities of solid,
liquid, and gaseous phases can be
described by their Gibbs free energies.
Thermodynamic models of each phase
can be used in conjunction with com-
puter-based Gibbs free energy minimiza-
tion routines to determine the phase
equilibria and thermodynamic properties
of each of the components, and the
JOM • November 2002
phases present in a chemical system
at equilibrium. A number of optimized
thermodynamic models are available
that can accurately predict phase
equilibria, volume percentage of solids,
and composition of residual liquid
at sub-liquidus conditions. 61,62 This
information is then substituted into the
various multiphase viscosity models to
obtain the predicted viscosities.
Clearly, if there are a large number
of calculations to be carried out, this
can be a time-consuming exercise.
Fortunately, a number of customized
phase equilibria-viscosity tools are now
becoming available.63–65 These tools
require only the key parameters—the
bulk composition of the slag, the effec-
tive oxygen partial pressure in the slag
phase, and the process temperature—to
be entered into a customized computer
interface, and the calculation procedure
is carried out automatically to predict
the viscosity properties of the resultant
liquid or mixture. The availability of
these models and design tools will
undoubtedly increase in coming years,
making it easier for practicing engineers
to select optimum process conditions
for their operations.
CONCLUSION
A number of important factors must
be taken into account in predicting the
viscosity behavior of a slag system;
paramount among these are the need to
accurately characterize the composition
and phase assemblage of the slag and to
select appropriate viscosity models that
have been optimized and verified over
the range of conditions of interest.
As a final comment, it should be
pointed out that the accuracies of the
viscosity models that are available can
only be as good as the original experi-
mental data. Inspection of experimental
data obtained recently from a number
of laboratories using identical slags14
demonstrated that even for well-
characterized slag systems, absolute
viscosity measurements differ by 25%.
In many slag systems, the uncertainties
in the experimental data are much
greater than this.
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A. Kondratiev is a research scholar, E. Jak is a
research director, and P.C. Hayes is a director with
the Pyrometallurgy Research Centre, School of
Engineering at the University of Queensland.
For more information, contact P.C. Hayes, University
of Queensland, Pyrometallurgy Research Centre,
School of Engineering, Brisbane 4075, Australia;
+61-7-3365-3551; fax +61-7-3365-3888; e-mail
P.Hayes@minmet.uq.edu.au.
45