Secondary Steel Making

PROBLEMS WITH BOF STEEL

Poor quality
Recent requirements
• CHEMISTRY
DEPENDENT PROPERTIES STRINGENT DEMANDS ON STEEL
• INHOMOGENEOUS BATH
• FORMABILITY QUALITY
• DISSOLVED GASES
CONSISTENCY IN PHYSICAL
• TOUGHNESS
PROPERTIES
• WELDABILITY
BOF PROCESS INCAPABLE TO SUPERIOR PRODUCTS FOR
• CORROSIVE BEHAVIOUR
CONTROL SOPHISTICATED APPLICATIONS

• SULPHUR EXTREMELY LOW LEVELS OF

RESIDUALS
• NITROGEN
• HYDROGEN
• OXYGEN
 FUNCTIONS OF SECONDARY STEEL OBJECTIVES OF SECONDARY
PRE-REQUISITES
MAKING STEELMAKING

• HOMOGENISATION OF • LOW S,P AND N FROM BOF DEOXIDATION - REMOVAL OF

TEMPERATURE AND OXYGEN

• PREVENTION OF CARRY OVER
COMPOSITION DESULPHURIZATION - TO SULPHUR
SLAG
CONCENTRATIONS AS LOW AS 0.002%
• ALLOYING • ADEQUATE SUPER HEAT FROM
ALLOYING - ADDITION OF
• DEOXIDATION BOF
ALLOYING ELEMENTS
• REMOVAL OF NON METALLIC • GOOD QUALITY OF FLUXES MICRO CLEANLINESS - REMOVAL OF
INCLUSIONS • GOOD QUALITY OF FERRO ALLOYS NON METALLIC INCLUSIONS

• MODIFICATION OF NON • HIGH PURITY ARGON INCLUSIONS MORPHOLOGY- CHANGING

METALLIC INCLUSIONS THE COMPOSITION OF REMAINING

• USE OF BASIC LINED LADLES
IMPURITIES TO IMPROVE THE
• REMOVAL OF GASES LIKE H 2 AND • ADEQUATE LADLE FREE BOARD
MICROSTRUCTURE OF THE STEEL
N2
• PROVISION FOR AI FEEDING SUPERHEAT CONTROL - +/-5 DEGREE C
• GRAIN REFINING
 INCLUSIONS IN STEEL

• Compound of metals (iron, manganese, silicon) with non-metals (oxygen, sulphur, nitrogen,
hydrogen, phosphorus), which may be present in steel, termed non-metallic inclusions. It forms
separate phases. According to their composition, non-metallic inclusions are usually classified as
follows:
On the basis of Chemistry :
I. Sulphides (FeS, CaS, ZrS2 etc. )
II. Oxides (FeO, MnO, SiO2, etc.)
III. Phosphates (Fe3P, FezP, etc.)
IV. Nitrides (NiN, ZrN, VN, etc.)
V. Carbides (Fe3C, Mn3C, W3C,WC, etc.) and
VI. Complex inclusions: silicates, oxysulphides (MnsPbO2), Carbonitride, etc.; the bulk of inclusions
in steel very often relate to this particular group.
• Non-metallic inclusions in steel are the cause of dangerous and serious material defects such as
brittleness and vide variety of crack formations.
• However, some of these inclusions can also have a beneficial effect on steel properties by
nucleating acicular ferrite during the austenite-to-ferrite phase transformation, especially in low-
carbon steels.
 STEEL PROPERTIES INCLUSION IN STEEL

• TENSILE STRENGTH
• DEFORMATION (DUCTILITY)
• TOUGHNESS
❖ BASIS OF CHEMISTRY
• FATIGUE STRENGTH
❖ BASIS OF SOURCE
• CORROSION RESISTANCE
• WELDABILITY
• POLISHABILITY
• MACHINABILITY
 ON THE BASIS OF SOURCE

• MECHANISM OF INCLUSION FORMATION :

Indigenous inclusions are formed in liquid, solidified, or solid
steel due to chemical reactions (deoxidation, desulfurization)
between the elements dissolved in steel.
Exogenous Inclusions are derived from external sources such
as furnace refractories, ladle lining, mold materials, etc.

• SOURCE OF INCLUSION:
I. Primary Inclusions: generated during deoxidation
reaction.
II. Secondary Inclusions: generated due to equilibrium
shift as temperature decreases during vessel transfer,
such as tapping and teeming operations.
III. Tertiary Inclusions: generated due to the process of
solidification, usually characterized by rapid cooling.
IV. Quaternary Inclusions: generated during solid-state
phase transformation, which causes changes in
solubility limits various constituents.
❑ MICRO INCLUSION: 1-100 µ m
❖ Beneficial as they restrict grain growth, increase yield strength and hardness
❖ Act as Nuclei for precipitation of carbides and nitrides
❑ MACRO INCLUSION : >100 µ m
❖ Harmful in nature so must be removed

❑ THE PRINCIPAL SOURCES OF NON- METALLIC INCLUSIONS IN STEEL ARE AS FOLLOWS :

1. Inclusions present in the charge materials: pig iron and scrap;
2. Inclusions passed to the metal from the lining of the furnace, launder, ladles, etc. due to
washing off of the lining by molten metal
3. Inclusion formed due to steel making process by interaction between metal and slag: on
addition of deoxidants or alloying elements, by precipitation from solidifying steel (due to
decrease in solubility or temperature).
 INCLUSION MODIFICATION Ca-TREATMENT FOR INCLUSION MODIFICATION

❖ Depends on the application, the inclusion • Mainly Al2O3 and MnS inclusions are modified
• (Al2O3) are solid at casting temperature & brittle in nature.
Modification technique is based on the design
of inclusions so as to minimize their harmful • Ca is widely used to modify inclusion
• Solubility of C in steel is 320ppm at 1600°C
effects on the product properties. • Density of Ca: 1.55g/cm³
❖ Uniformly dispersion of inclusion in the matrix. • Melting Temp. of Ca: 1439 °C
• Form vapour at steel temperature 1600 °C
❖ It should have a high chemical affinity for the • MnS inclusion in steel deformation becomes stringer type.
inclusions.
Compound Melting temperature (°C) Ca/Al
❖ It should be able to modify the composition so Al2O3 2050 ----
that it becomes liquid. CaO, 2 Al2O3 1727 0.37
❖ It should be able to modify the shape i.e., CaO, Al2O3 1595 0.74
sharp edges and corners of inclusion to 12CaO, 7 Al2O3 1400 1.27
spherical. 3CaO, Al2O3 1527 2.22
CaS 2000 -----
MnS 1620 ----
 PROCESSING OF STEEL THROUGH LADLE FURNACE
1 st Step 2 nd Step

• Prior information Argon purging and arcing are

Heat No. done for an initial 5 minutes
Steel grade homogenizing the bath

Tapping Time composition and temperature.

Temperature is then measured
Tapping temperature
and a sample is sent to process
Argon temperature
control for analysis.
Argon Purging time

3 rd Step 4 th Step
The data is collected within 5 Argon purging is started, addition of required petro-
minutes. Based on the data, the coke, silico-manganese and ferrosilicon, and other
temperature & chemistry, the alloys is done to achieve the temperature. The final
degree of heating, and alloy temperature and metal sample is taken and heat is
addition required to achieve aim dispatched after the addition of required
chemistry is decided. materials(LCC).
 CLASSIFICATION

Depending on the desired end result the secondary refining processes have
been broadly classified into:
STIRRING PROCESS: Gas Rinsing, Gas rinsing with synthetic slag treatment
INJECTION PROCESS: Powder, wire
VACUUM PROCESS: Ladle Degassing, Recirculation degassing
 Stirring & Homogenization

Ladle stirring is an essential operation during

secondary steelmaking in order to:
▪ Homogenize bath composition
▪ Homogenize bath temperature
▪ Facilitate slag-metal interaction essential for
processes such as desulfurization.
▪ Accelerate the removal of inclusions in the steel
In practice, stirring is achieved by:
• Argon bubbling through the liquid steel, either via a
submerged lance, or by porous plugs in the bottom
of the ladle;
• Electromagnetic Stirring-EMS
 SPECIAL INJECTION PROCESSES

INJECTION OF DESULFURIZING AGENTS (Ca, Mg,CaSi, CaC 2, CaF2+ CaO) to a molten steel is the most
effective method of sulfur removal. Injection methods usually combine the supply of a dispersed
desulfurizing agent (powder) with stirring by argon blowing.
A ladle with molten steel (deoxidized, killed)is transported to the injection stand where it is placed under a
cover, through which the injection lance may lower and immerse in to melt. Steel treated in the stand is
covered by a layer of desulfurizing slag having high solubility of sulfur and capable to absorb sulfides
formed as a result of active agents injection.
Desulfurization agents are injected in the argon stream. Argon bubbles produce stirring of the molten steel
and the slag promoting desulfurization. Stirring also provides thermal and chemical homogenization of the
melt.
Wire feeding is also useful for additions that:
• Are less dense than molten steel and might otherwise
float to the surface;
• Have limited solubility;
• Have a high vapor pressure;
• Have a high affinity for oxygen;
• Are very expensive and /or added in very small
quantities;
• Are toxic ;
Aluminium is often added by wire feeding to improve
recovery rate, control of Al content and improve steel
cleanness.
▪ Solubility of gases decreases in molten metal as temp decreases during solidification.
▪ Degassing works on Sieverts Law. ( % Gas Dissolved in liquid is directly proportional to under root of partial pressure)
▪ By reducing pressure on molten metal from 1 atm pressure( room atm ) to vacuum level .

▪ Hydrogen tries to escape from metal

by forming pin holes during
solidification. It can be observed by
Ultrasonic test.
▪ Hydrogen embrittlement (Steel can
not sustain high load)

Deoxidation: Deoxidation is a method used in metallurgy to

remove the oxygen content during steel manufacturing.
aluminum, silicon, and manganese are the most common
deoxidizers used in steel production.
Killed Steel: Killed steel is steel that has been completely
deoxidized by the addition of an agent before casting such that
there is practically no evolution of gas during solidification.
1. Oxygen enters during oxygen-blowing

2. Atmosphere (21% O 2 ) during tapping

3. Scrap is rusted
Why removal of O2 :
1. Creats blow hole by forming CO, CO2 during solidification
2. Oxygen may react with other impurities like Mn, Si, Fe, etc and form oxides &
trapped inside metal as inclusions.
Removal of O 2 :
1. By using Deoxidiser (Si, Mn, Si, Ca) after primary steel making (Just opposite of primary steel
making), or the addition of aluminium during tapping from BOF to ladle.
2. Vacuum Degassing
Removal of N2 (79% in air), H2 ( moisture in air allowH2)
Fe, Al , Si these form nitrides by nitrogen which form brittle phase of nitride & increase strain
hardening effect in steel. It will reduce ductility & will create problems during deep drawing
 PRINCIPLES OF VAD PROCEDURE OF VAD

• Vacuum treatment consists of

• Ladle is placed inside the vacuum tank
exposing liquid steel to a low- • Argon purging
pressure environment. • Arcing by electrodes
• The vacuum tank is evacuated
• The equilibrium solubility of • Temp. and steel sample collection.
diatomic gases like H2 and N2 in • Ferro alloy to achieve the aim
chemistry .
steel is given by the Sievert’s • Ladle is dispatched to CCS for casting
Law as:
% Gas Dissolved =k √p
p= Partial Pressure of the gas in ambient
atmosphere
K= Sievert’s Constant
 Benefits of Ladle Degassing (VD, Tank
Degassing)
Hydrogen removal (degassing)
Oxygen removal (deoxidation)
Deep Sulphur removal (desulfurization)
Carbon removal (decarburization)
Precise alloying;
Non-metallic Inclusions (oxides and
nitrides)removal;
Temperature and chemical
homogenizing.

Degassing of structural (TMT bar)& normal

steel (low & medium carbon steel)
Latest Degasser: RH Degasser for high quality of steel

RH DEGASSER

ADVANTAGES
• Dissolved Gases in liquid Steel is reduced.
• Reduced the hydrogen concentration level to less than
1.6 ppm in RAIL-STEEL
• Removal of Non–metallic Inclusions during Process.
• To improve cleanliness by removing oxygen in the form
of CO Gas.
• To ensure better control of chemical composition and
temperature.
• Alloy addition can be made to adjust the specification
Modern stainless steelmaking practice does not attempt to make stainless steel in
an EAF alone.
The EAF is used to provide a molten steel charge for converters without any significant
decarburisation of the melt and with minimum chromium oxidation to the slag. The melt is then
decarburised in a variety of converters, with argon oxygen decarburisation (AOD) and vacuum
oxygen decarburisation (VOD) being the most widely used.
As a result, these practices are classified as ‘duplex’ in that there are two stages in the production
of stainless steels which have very low carbon and nitrogen requirements and this is known as
‘triplex’ practice.
The duty of the EAF is to efficiently and economically deliver molten metal of the required
composition and temperature to a converter (as like AOD, VOD).
 Steps for AOD
1. Heat is transfered from primary steel
making to AOD Process.
2. In this AOD Fe –Cr added to maintain
12% Cr. Now in this heat it contains Cr
& C.
The main aim to remove carban &
maintain the cr composition., for this
purpose blowing Ar- O2 gas mixture.
Then partial pressure of Co gases
reduces which will be helpful in
reducing the oxidation of chromium.
3. Modern AOD Ar- O2 gas can be supplied
from top & bottom.
4. Initially Ar: O2 ratio 1:3 as
decarburization proceeds, and in the
last stage of blowing Ar: O2 ratio will
be 3:1.
5. Last stage Ni & other alloying additions
can be added.
6. 2 Cr2 O3+3 Si= 4Cr+3 Si O 2
 ADVANTAGES

✔ Extensive decarburization with low

chromium losses.
✔ Flexibility to use high-carbon alloying
material of lower cost.
✔ High rate of chromium recovery by proper
additions.
✔ Chemical heating of liquid steel.
✔ Improved conditions for desulfurization by
proper additions.
✔ Improved conditions for inclusion flotation.
Benefits of Vacuum Oxygen
Decarburization (VOD)
• Deep carbon removal (decarburization)
• Low steels of chromium in the
treatment of stainless steel; Hydrogen
removal (degassing);
• Sulfur removal (desulfurization); 1. 1 st step Decarburization: As O2 blowing starts carbon
• Precise alloying; reacts to form Co and immediately this CO gas is sucked
• Reheating-Non metallic inclusions by a vacuum pump.
(oxides and nitrides) removal; 2. Ar purging is required to remove carbon from the
• Temperature and chemical bottom level of the container by stirring.
homogenizing. 3. 2 nd Step Reduction: 2 Cr2O3+3 Si= 4Cr+3 SiO2
4. Deoxiation by added aluminum, Si, etc for removing
oxygen
5. Desulphurization by adding Cao
S+Cao=Cas +O
❖ Hot Rolling of Steel

Terminology :
❖ Bloom is the product of ingot (cross-sectional
area>230 cm 2)
❖ Billet is the product obtained from a further
reduction by hot rolling
❖ Slab is the hot rolled ingot
Plate is the product with a thickness >6mm
Sheet is a product with a thickness of <6 mm and a
width of> 600mm
Strip is the product with a thickness <6mm and
width <600 mm.
The End