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Sulfur in steel
Sulfur in steel
Sulfur (S) may dissolve in liquid iron (Fe) at any concentration. However solubility of sulfur
in solid iron is limited: 0.002% in -iron at room temperature and 0.013% in -iron at 1832F
(1000C).
When a liquid steel cools down and solidifies the solubility of sulfur drops and it is liberated
from the solution in form of iron sulfide (FeS) forming an eutectic with the surrounding iron.
The eutectic is segregated at the iron grain boundaries. The eutectic temperature is relatively
low - about 1810F (988C).
Fe-FeS eutectic weakens the bonding between the grains and causes sharp drop of the steel
properties (brittleness) at the temperatures of hot deformation (Rolling, Forging etc.).
Brittleness of steel at hot metal forming operations due to the presence of low-melting iron
sulfides segregated at grain boundaries is called hot shortness.
In order to prevent formation of low-melting iron sulfide manganese (Mn) is added to steel to
a content not less than 0.2%.
Manganese actively reacts with iron sulfides during solidification of steel transforming FeS to
MnS according to the reaction:
(FeS) + [Mn] = (MnS) + Fe
(square brackets [ ] - signify concentration in steel, round brackets ( ) signify concentration in
slag)
The melting temperature of manganese sulfide is relatively high - about 2930F (1610C)
therefore the steels containing manganese may be deformed in hot state (no hot shortness).
Unfortunately MnS inclusions are:
All these factors determine negative influence of sulfide inclusions on the mechanical
properties. Cracks may be initiated at brittle sharp edge inclusions. Sulfide inclusions
especially arranged in a chain form also make easier the cracks propagation along the grain
boundaries.
The negative effect of sulfur on the steel properties becomes more significant in large ingots
and castings, some zones of which are enriched by sulfur (macrosegregation of sulfur).
The properties negatively affected by sulfur:
Ductility;
Impact toughness;
corrosion resistance;
Weldability.
coefficient of sulfur:
LS = (S)/[S]
Where:
(S) - concentration of sulfur in slag;
[S] - concentration of sulfur in steel;
As appears from the above equations desulfurization is effective in deoxidized (low (O))
basic (high (CaO)) slags. Therefore ability of Basic Oxygen Process (BOP) to remove sulfur
is low due to its highly oxidized slag.
Desulfurization may be effectively conducted in the reducing slag stage of the steel making
process in Electric-arc furnace. At this stage the oxidizing slag is removed and then lime flux
is added to form basic slag with high CaO content.
Deep desulfurization by slags may be achieved in ladle:
The refining (desulfurizing) slag with high content of CaO and no FeO is prepared
and placed in an empty ladle.
The molten steel is poured into the ladle filled with the refining slag.
Energy of the falling steel stream causes mixing the slag with the steel, during which
sulfur is removed from the steel to slag phase.
CaSi;
CaC2;
CaC2 + Mg;
Ca + Al;
Ca;
Mg.
The desulfurizing agents are injected into molten steel either in form of powder transported
by an argon blown to the steel through a lance or in form of a cored wire containing powder
of desulfurizing agent. In the latter method stirring by argon bubbling from the porous plug
mounted in the ladle bottom is used.
Chemical reactions between desulfurizing agents and sulfur dissolved in steel may be
presented by the following equations:
Ca + [S] = (CaS)
Mg + [S] = (MgS)
Injection of desulfurizing agents allows to achieve ultra-low concentrations of sulfur in steel
(0.0002%).