Why Control Sulfur Content?

Sulfur MnS

is present in solid steel as manganese sulfide (MnS) inclusions

inclusions affect the processing and properties of steel Effects are detrimental, as these inclusions are more plastic than steel and, hence, during deformation they act as crack initiation sites and zones of weakness

Their volume fraction, size, shape and distribution depend on the sulfur content, oxygen content, solidification rate, degree of hot and cold deformation and hot working temperatures

Sulfur

is detrimental to ductility, toughness, formability, weldability and corrosion resistance sulfur is beneficial to machinability

Sufficient manganese must be present in the steel to prevent the formation of iron sulfide, which is highly detrimental to hot workability and leads to severe cracking during hot rolling (hot shortness).

Elongated MnS inclusions

Sulfur Specifications The most demanding applications of steel require the sulfur levels to reduce to very low levels (<0.001% S) in order to achieve the required combination of strength, ductility, formability and weldability
(For applications which are extensively machined during manufacturing higher sulfur levels are required)

%S 0.300 0.070 0.030 0.015 0.0050 0.0015 0.0010 0.0010 Hydraulic connectors Crankshaft Gear Spanner High Strength Car Wheel Sub-frame assembly Linepipe for Sour service Aircraft undercarriage

Removal of Sulfur The sulfur content from the BOS or EAF is typically 0.01 - 0.02% To satisfy the low sulfur specifications is necessary to remove sulfur from the steel during secondary steelmaking

Sulfur is removed by slag-liquid metal reactions under reducing conditions in which sulfur is transferred from the steel through the slag-metal interface and into the slag The basic chemical reaction in desulfurization is: 3(CaO) + 2[Al] + 3[S] 3(CaS) + (Al2O3)

( ) in slag and [ ] in steel.

The partitioning (Ls) between the sulfur in the slag (S) and steel [S] is given by:

Cs : The sulfur capacity of the slag a0 : Activity of oxygen in the steel

Slags for Desulfurization Slag : An ionic solution of various oxides and fluxes Several functions :

Protects liquid steel from reactions with the atmosphere reducing pick-up of nitrogen and hydrogen thermal insulation It reacts with refractories causing refractory wear reservoir for inclusions (refining medium for desulfurization, deoxidation and dephosphorization )

The composition of the slag during secondary steelmaking has to be controlled very carefully to achieve the required inclusion content and steel composition

Slag important factors controlling the reactions with steel and refractorie :
Density, volume (depth), melting point, viscosity and interfacial energy of the slag

Desulfurization Slag Slag from the primary steelmaking furnace (BOS/EAF) : 45% CaO - 23% FeO - 15% SiO2 - 8% MnO - 7% MgO 2% P2O5 Basic slag contains free oxygen ions encouraged by the presence of CaO and MgO Acid slags deficient in O2 and contain SiO2 and P2O5

The basicity (B) of slag is defined as:

A high slag basicity is required for desulfurization

Reference to the CaO-Al2O3-SiO2 at 5% MgO ternary diagrams at 1600 C and 0.03% Al, with a superposition of the sulfur partition ratio (Ls) values reveals the slag compositions suitable for high degrees of desulfurization.

Kinetics of Desulfurization I Reaction has to occur quickly to be economically viable These factors encourage fast desulfurization : High sulfide capacity of slag

High temperature Stirring of liquid metal Vacuum Low viscosity ( The most important factor )

Kinetics of Desulfurization II The degree of desulfurization is given by:

where

ks ~ 0.0013 0.25 for < 60 W tonne1 ks ~ 8.1 106 2.1 for > 60 W tonne1
St Sulfur at time t in steel S0 Sulfur at time 0 in steel Ks rate constant t time Ls Sulfur coefficient (%S)/[%S] Wm Mass of steel Ws Mass of slag stirring power

Stirring energy / W tonne-1

Other Factors : Refractories Which type of ladle gives best desulfurization? Magnesite.Yes ,but expensive

Fireclay..No ( Fireclay is Silica rich ) Dolomite.Yes ( Dolomite is lime rich )

High slag basicity is needed for desulfurization basic refractory is needed

Ladle Stirring

There are several techniques for stirring the liquid metal in the ladle.

Desulfurization: Self Assessment Exercise Addition should be made for desulfurization : CaO Al Al2O3 CaF2 - Ar

Calcium Injection I Calcium is a powerful desulfurizer and deoxidizer Added to the ladle as a cored wire containing calcium metal - CaSi - CaSi powder
( Calcium is rarely used as a deoxidizer in its own right as it is more expensive than other deoxidizers )

Calcium boiling point :1491 C Is lower that the melting point of steel Is a vapor Introduce calcium or its compounds as deep into the ladle as possible when added to steel Ferrostatic pressure prevents it from vaporizing

Calcium Injection

Calcium Injection II Calcium effects : Modifies the shape of sulfide inclusions at low sulfur levels

Enhances machinability Makes them more globular Reduce the detrimental effect of sulfur on ductility and toughness

modifies alumina inclusions to a molten calcium

aluminate phase which prevents nozzle blockage by alumina