Slag, Matte and Dross

Structures
Dr. Ahmet TURAN
Yalova University
Chemical & Process Engineering Dpt.
March 2020

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Formation of immiscible molten
layers
• During the melting of an ore or concantrate, the
silicates, sulfides, arsenides, and metals produced
coalse, each forming an individual molten layer.
• Because of the differences in specific gravity, it is usually
possible to allow the material to settle and to separate
each layer.
• The silicate layer on the top is called slag, the sulfide
layer next is called matte, and the arsenide layer next, is
called speiss [1].

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Different layers formed when melting lead oxide
(obtained by the oxidation of a lead sulfide concentrate)
in the presence of carbon to get impure metallic lead
called bullion [1].
Phase Specific gravity Common name Metal present
Major Minor
Silicate 3.6 Slag Ca, Si, Al, Mg, Mn, Sn
Zn, Fe
Sulfide 5.2 Matte Cu Fe
Arsenide 6.0 Speiss As, Sb Co, Ni
Metal 10.0 Bullion Pb Au, Ag

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 Slag

Matte

Slag

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Slags
• In pyrometallurgy, SiO2 is considered an acidic oxide and
CaO as a basic oxide.
• The concept was introduced long ago when it was
observed that some oxides dissolve in water forming an
acid, and others when dissolved form a base.
• Although SiO2 is insoluble in water, it was regarded as
the anhydride of various silicic acids (ortho H4SiO4, meta
H2SiO3 and poly H4SiO8).
• P2O5 + 3H2O → 2H3PO4
• CaO + H2O → Ca(OH)2 [1].

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 Some non-ferrous
metal slags

Blast Furnace Slag

Some non-ferrous
EAF Slag metal slags
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Fluxes
• To facilitate the melting point process, a flux is usually added to
combine with the high-melting point components and form the
slag having a low melting point.
• For example, an ore containing limestone as gangue mineral
when heated will result in the formation of CaO which has a
melting point of 2580 ºC degrees celcius.
• If, however, a flux such as silica (melting point 1728 ºC) is added
to the ore, then on heating, a reaction between CaO and SiO2 will
take place to form calcium silicate, i.e., a slag whose melting point
may be as low as 1500 ºC (e.g. non-ferrous slags).
• In this way the gangue minerals are separated from the other
valuable ore components in the form of a low-melting slag.
• If on the other hand, the gangue mineral was SiO2, then CaO
should be added as a flux to aid in the formation of slag (ferrous
slags) [1].

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Simplified phase diagram of SiO2 – CaO system [1].
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 Slag acidity
• Silicates are the chief components of slags in ferrous and nonferrous metallurgy.
Silicon dioxide forms a number of silicic and polysilicic acids, whose salts are the
silicates contained in slags. A general formula for all silicic acids is nSiO2 . mH2O,
whereas silicates are described by a formula nSiO2 .mMeO.

• This form of describing chemical compounds puts in relief the amount of each
particular oxide composing a given silicate. In metallurgy, stoichiometric ratios are
described by a degree (or coefficient) of acidity or basicity. The degree of acidity n
is defined as the ratio of the number of atoms of oxygen, combined with silicon in
silica, to the number of atoms of oxygen combined into basic oxides [2, 3].

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By degree of acidity, the slags are called:

1- Monosilicates: 2FeO.SiO2; CaO. FeO. SiO2, in which n = 1.

Monosilicates, irrespective of their compositions, frequently have similar properties
(melting point, viscosity, etc.);
2- Bisilicates: FeO. SiO2; 0.5CaO . 0.5 FeO . SiO2in which n = 2;
3- Trisilicates, etc.

Fractional acidity is also possible, as n= 1.5 (one-and-a-half silicate), n= 0.5

(subsilicate); it is expressed practically by any number ranging from n= 0.5 to n= 5.

The degree of acidity of a slag may be calculated from its compositions, expressed in
per cent (by mass). First, convert the “mass” per cent into molecular ones, then
describe slag compositions by stoichiometric formula, and, finally, calculate the
degree of acidity.

For example, the calculation of the degree of acidity of a slag containing 44% SiO2,
36% FeO and 10% CaO, involves the following steps [2, 3]:

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SiO2: 44/60 = 0.73 mole, or 0.73 . 2 = 1.46 g-atom of oxygen, i.e.
1.46 g-atom of oxygen is combined in the form of SiO2.
FeO: 36/72 = 0.5 g-atom;
CaO: 10/56 = 0.17 g-atom,

0.5 + 0.17 = 0.67 g-atom, i.e. 0.67 g-atom of oxygen is combined with the bases.
The degree of acidity is then n = 1.46 / 0.67 = 2.1

Silicates of an acidity close to 1 have low viscosity and melting point, whereas
silicates of n = 2.5 to 3, a high melting point and a high viscosity.

Thus, slag properties are a function of their acidity. Al2O3 and other amphoteric
oxides are not taken into account when calculating the acidity of a silicate slag.

The degree of basicity or the basicity of a slag is the ratio of the number of moles of
basic oxides to the number of moles of silica.

For example, the degree of acidity in

2CaO.SiO2, FeO.CaO.SiO2, 0.5FeO.1.5CaO.SiO2 compounds equals 2;
for CaO.2SiO2, 0.5FeO.0.5CaO.2SiO2 it is equal to 0.5 [2, 3].
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Basicity Degree
The degree of basicity of a slag is the molar number of available basic
oxides divided by the number of moles of silicon dioxide [2, 3].

For a slag containing 44% SiO2, 36% FeO and 10% CaO

= 1.178

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CaO – SiO2 phase diagram (ferrous slags) [4].

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FeO – SiO2 phase diagram (non-ferrous slags) [5]

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Matte structures [3]

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Dross Aluminium dross is produced in
primary and secondary plants.
It is the raw material for aluminium
dross recovery plants [6].

The aluminium dross is basically divided into two types:

- White drossHigh metallic Al content (up to ~45wt.%)
- Black drossLow metallic Al content (up to ~25wt.%)
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Dross is obtained in pyrometallurgical operations of light metals such as the Al and the Mg and,
it is the mixture of metals, metal oxide, metal nitride and halide-based compunds [6, 7].

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References
1. Fathi Habashi, Principles of Extractive Metallurgy – Volume:3
Pyrometallurgy, Gordon and Breach, New York, 1985.
2. Onuralp Yücel, Chemical Metallurgy Lecture Notes, ITU,
Istanbul, Turkey, 2020.
3. Fuat Yavuz Bor, Ekstraktif Metalurji Prensipleri – Kısım II, İTÜ
Matbaası, 1989, İstanbul.
4. V.D. Eisenhuü̈ttenleute (ed.): Slag Atlas, 2nd ed., Verlag
Stahleisen GmbH Düsseldorf, 1995, p. 359.
5. R. A. Cruz, S. A. Romero, R. M. Vargas and L. M. Hallen: J. Non-
Cryst. Solids, 351 (2005), 1359.
6. Umay Çınarlı, Yalova Uni. MSc thesis, 2020, Yalova, Turkey.
7. B.R. Das et al., Production of η-alumina from waste aluminium
dross, Minerals Engineering 20 (2007) 252–258.

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