Secondary Metallurgical

Processes

Asst. Prof. Dr. C. Fahir Arısoy

1
 Steel Production Processes
Steel Scrap
Crude Iron
Secondary Metallurgy

Iron Ore
Coke
Fluxes

BOF

Blast Furnace

Steel Scrap
Fluxes
Electricity

2
EAF Continuous Casting
Oxygen in Steel

• The amount of Oxygen in the steel depens on the carbon

ratio and casting the temperature.

After BOF 0.02% - 0.2 of oxygen remains in the steel,

Remaining oxygen is in the form of FeO.

Steel production processes are applied at about 1600°C

temperatures.
There is a equilibrium ratio of (FeO) / [FeO] = 4.4 at
temperatures about 1600°C.

In liquid steel at 1600°C ; [%O] = 0.02 min

3
• DEOXIDATION

FeO reacts with C and the reaction continues in the crucible.

Reaction takes place Carbon with iron oxide, can be regarded as the
main-first deoxidation reaction.
[C] + [FeO] = CO (g) + [Fe]

This equilibrium depends on ;

• temperature,
• composition of the slag
• composition of steel.

Mold steel solidifies with the continuation of this reaction, and after
solidification is completed rimmed steel ingots are produced.
4
• Rimmed steel ingot: The gas spaces occurs in steel ingots.
• The control of this reaction is difficult for Steels containing more
then 0.25% carbon. Therefore further deoxidation process is
performed with deoxidizer elements at the final stage of steel
production.

Rimmed steel;Low-carbon steel, partially deoxidized

Killed steel fully deoxidized by deoxidizer elements 5
The amount and type of deoxidizer added determines the type of steel. If sufficent
deoxidizers are added, no gas is evolved from the solidifying steel, and the steel
is said to be “killed.” The ingot drawing labelled number 1 shows a fully killed
(deoxidized) steel showing only a shrinkage cavity, and no bubbles or porosity.
( This shrinkage cavity would be cropped off in normal rolling practice.) 6
The dotted line indicates the height to which the steel originally was poured
in each ingot mold. Depending on the carbon content and particularly of the
oxygen content, the ingot structures range from that of a fully killed or
dead-killed ingot No 1 to that of a violently rimmed ingot No 8.
Included in the series are indicated in figure 1 i.e. killed steel No 1,
semikilled steel No 2, capped steel No 5, and rimmed steel No 7. 7
Metallic deoxidizers

Deoxidizer elements which;

• have higher oxygen affinity than iron or
• Thermodynamically more negative formation free energy
(ΔG) of their oxides than iron oxides.

• The deoxidation of steel is usually performed by adding

Mn, Si and Al.

8
9
• The deoxidation of steel is usually performed by
adding Si, Mn, Al.
• Wires containing ferro alloys and granulated Ca
used in secondary metallurgy processes today.
• Elements are added into liquid steel in the form of ;
ferro–silicon, ferro-manganese, granulated Al and Ca,
Al wire, Al ingot or AlSiFe alloy, and ferro-
aluminum.
• [FeO] + [C] = Fe +CO
• [FeO] + [Mn] = Fe + (MnO)
• 2[FeO] + [Si] = 2Fe + (SiO2)
• 3[FeO] + 2[Al] = 3 Fe + (Al2O3)
10
Deoxidation is performed in different steps
according to oxygen concentration level
• There is always some amount Si and Mn are
present in steel as alloying elements.
• Therefore,
the first deoxidants are Si and Mn and the
final deoxidant element is Al.

• Aluminum prevents aging of steel and it is a

grain refiner for final structures of steel.
11
STEEL REFINING OPERATIONS

• Today, new steel processes make possible to

produce very low impurity containing steel at a
lower cost.

• Ladles are used as combined with a degassing

refining unit (ladle processes).
• Processes have great advantages in the
development of different grades of steel.

12
With ladle metallurgy processes;

• impurity rates reduced significantly

• removal of inclusions became possible
• impurities; such as oxygen, sulfur, nitrogen,
phosphrus and in most cases carbon can be
reduced to very low levels.
• became possible to produced Steel in narrow
range of chemical composition limits.
• Flux consumption, time and energy saving
became possible with new final stage refining
Technologies.
13
• Refining process operations made in a ladle or
same type of a container; these operations are
also named as «Ladle Metallurgy».

• Here the ladle is not just a crucible for the

transport of liquid metal to the casting station,
it is also used as a large scale refining
operation unit.

• This is one of the last station in order to

improve the quality before casting in steel
production. 14
15
16
ladle metallurgical operations are applied commonly
to the following subjects:

1. The addition of alloying efficiently and more

efficient control of composition in narrow limits.
2. effective deoxidation
3. Homogenization of the temperature and the
composition.
4. inclusion flotation
5. dephosphorization
6. desulphurization
7. Sulfide shape control
8. Oxide form control
9. hydrogen, oxygen, nitrogen gas removal in
vacuum. 17
18
• The simplest form of Ladle Metallurgy operations
are mixing of alloying elements to steel and
adjustment of the composition.

• the mixing performed by gas bubbles which are

passed through porous brick at the bottom of
laddle or immersed lances in liquid.
• Argon gas is widely used as the inert gas.
• Gas bubbles provides gas flow and temperature
homogenization, as well as provide mixing of
alloying elements.

19
20
• Ladle contains a cover and immersing lance into liquid
metal through the slag
• Inert gas prevents the oxidation of the molten liquid
• Refining elements are added to the metal bath by using
snorkel

21
22
Gas-stirring of ladle during desulfurization 23
 Vacuum ladle degassing

Methods of vacuum ladle degassing utilize the reaction

of deoxidation by carbon dissolved in steel according to the
equation:

[C] + [O] = {CO}

Vacuum treatment of molten steel decreases the partial pressure

of CO, which results in the equilibrium reaction of carbon
oxidation.

Bubbles of carbon monoxide form in the liquid steel, float up and

then they are removed by the vacuum system.

24
Vacuum ladle degassing

In the Ladle Degassing method the

ladle with molten steel is placed
into a vacuum chamber.

The ladle is equipped with a porous

refractory plug mounted in the ladle
bottom. Through the plug argon is
supplied during vacuum treatment.

The Addition hopper is used for

adding alloying elements and/or
slag components.

The reaction
[C] + [O] = {CO}
starting in the steel under vacuum
conditions causes stirring, which is
additionally intensified by argon
blown through the bottom porous
plug to sweep out to gasses
25
•Vacuum Oxygen Decarburization (VOD)
In this method a conventional Ladle
Degassing (VD, Tank Degassing)
chamber is equipped with a vertical
water cooled lance for blowing oxygen
on the molten steel surface.

Vacuum Oxygen Decarburization

(VOD) method is used for
manufacturing Stainless Steel.

Oxidation of liquid steel components

under vacuum differs from that at
normal pressure: oxygen is consumed
mainly by the reaction
[C] + [O] = {CO}
rather than by oxidation of chromium,
which is the main alloying
element of stainless steels.

26
•Vacuum Oxygen Decarburization (VOD)

During decarburization reaction the

excess carbon binds with oxygen
and other gases are inflated.

This allows the formation of carbon

monoxide leading to get carbon
levels in the order of 0.015%.

The loss of Chromium by oxidation

is contained by the ratio calibrated
for oxygen and argon.

27
• The principle of vacuum oxygen decarburization is
removal of carbon in molten stainless steel by
reducing partial pressure of carbon monoxide gas
under vacuum condition.
• Carbon enters from high carbon ferrochromium and
from other source of carbon in charging materials.
• The key of the process is to prevent over oxidation
of chromium during oxygen blowing.

• The correlation between carbon content, chromium

content and partial pressure of carbon monoxide at
1600 °C is given in Figure

28
Chromium-carbon equilibrium at 1600 °C.

29
 Major Equipment Used in secondary metallurgy

Cored wire injection:

•This system capable to feed of Al and Ca

ferro alloys to steel bath in the required rate.
Wire feed is useful in case of:
•Has a limited (specified) solution
•High oxygen affinity;
•Can be added in very small amounts;

i.e. FeTi and FeB wire injection for austenitic

structure, Al and CaSi wire injection for ferritic
structures 30
• Cored wires: Chemicals which has high affinity
to oxidation are placed in the center of a wire
made of low carbon steel. These chemicals
descend down enough to the surface in the core of
the steel wire, and thus eliminates a serious loss of
oxidation.

31
32
Calcium (Ca) CaSi 30/60
CaSi Ba
CaSi 40/50
CaSi 60/30
CaSi 64
Pure calcium
CaFe 30/70
CaAlFe
Bismuth (B) BiCaCo3
Lead (Pb) Pb
Sulphur (S) S
FeS
Pyrit (FeS2)
Manganese (Mn) FeMn
Boron (B) Ferro-Bor
Chrome (Cr) FeCr 70
Carbon (C)
Niobium (Nb) FeNb
Nitrogen (N) CaCN2
FeMnN
Titanium (Ti) FeTi 70
Titanium sponge (Ti) Ti sponge
33
Vanadium (V) FeV
34
Refining Stages

• The first step of refining of oxygen from crude

steel in the ladle is applied with usually,
ferroalloys (ferromanganese, ferrosilicon,
manganese, etc.) and
• at the final stage oxygen is removed by
aluminum.

35
 Refining Stages
Ferromanganese, is used as deoxidizer element to reduce the
dissolved oxygen content of the steel to 100-200 ppm.

Semi deoxidizing of steel:

•Si / Mn is 50-70 ppm Oxygen.
•Si / Mn / Al is used in order to reduce oxygen to 25-40 ppm.
•Si / Mn / Ca is used to reduce oxygen to 5-20 ppm oxygen.
Deoxidizing of steel:
Al is used to reduced level of dissolved oxygen in the steel
to 2-4 ppm.

36
• It can be possible to reduce the sulfur rates as low as 20
ppm, just in case of ladle desulfurization process is
applied to killed steel in the presence of calcium
aluminate slag. The basic reaction is:
• [Al]+[S]+(CaO)=(CaS)+(Al2O3)

37
CONCLUSION
IN SECONDARY METALLURGICAL PROCESSES
• good mixing and heating for homogenization,
• vacuum degassing system for refining of non-metallic
impurities,
• additive usage for desulphurization and alloying,
• oxygen blowing lance to remove fast decarburization
and dephosphorization,
• deoxidazer addition systems in the vacuum deoxidation
chamber
required

38
 REMELTING REFINING PROCESSES
(TERTIARY METALLURGY)

1. Vacuum Arc Remelting (VAR)

• VAR is widely used to improve the cleanliness and refine the

structure of standard air-melted or vacuum induction melted
ingots, then called consumable electrodes.

• VAR steels and superalloys are used in a great number of high-

integrity applications where cleanliness, homogeneity,
improved fatigue and fracture toughness of the final product
are essential.

• Aerospace, power generation, defense, medical and nuclear

industries rely on the properties and performance of these
advanced remelted materials.
39
• Vacuum Arc Remelting (VAR)

• VAR is the continuous remelting of a consumable electrode by

means of an arc under vacuum.

• DC power is applied to strike an arc between the electrode and

the baseplate of a copper mold contained in a water jacket.

• The intense heat generated by the electric arc melts the tip of
the electrode and a new ingot is progressively formed in the
water-cooled mold. A high vacuum is being maintained
throughout the remelting process.

40
http://web.ald-vt.de/cms/vakuum-technologie/anlagen/vacuum-arc-remelting-var 41
 •Features
•Melt-down by electric arc
under vacuum of 0.004
mbar
•Evaporation of tramp
elements
•Utmost degassing
•Excellent cleanliness
•No risk of freckle
formation
•Extra-high accuracy of final
chemistry
•Ingot diameter from 300 to
1000 mm
•Ingot weight from 1 to 30 t

42
https://www.sms-group.com/plants/all-plants/tertiary-metallurgy/
• Vacuum Arc Remelting (VAR)

• The solidification rate of molten material can be tightly

controlled. This allows a high degree of control over the
microstructure as well as the ability to minimize segregation
• The gases dissolved in liquid metal during melting metals in
open furnaces, such as nitrogen, oxygen, and hydrogen are
considered to be detrimental to the majority of steels and
alloys.
• Under vacuum conditions these gases escape from liquid metal
to the vacuum chamber.
• Elements with high vapor pressure such as carbon, sulfur,
and magnesium (frequently contaminants) are lowered in
concentration.
• Centerline porosity and segregation are eliminated.
• Certain alloys cannot be melted in open air furnaces

43
2. Electro Slag Remelting (ESR)

• Whereas VAR needs vacuum for refining, in ESR the consumable

electrode is dipped into a pool of slag in a water-cooled mold.

• An electric current (usually AC) passes through the slag, between

the electrode and the ingot being formed and superheats the slag
so that drops of metal are melted from the electrode.

• They travel through the slag to the bottom of the water-cooled

mold where they solidify. The slag pool is carried upwards as the
ingot forms.

44
• Slags for ESR are usually based on calcium fluoride (CaF2), lime
(CaO) and alumina (Al2O3). Magnesia (MgO), titania (TiO2) and
silica (SiO2) may also be added, depending on the alloy to be
remelted.
To perform its intended functions, the slag must have some well-
defined properties, such as:
• Its melting point must be lower than that of the metal to be
remelted;
• It must be electrically efficient;
• Its composition should be selected to ensure the desired chemical
reactions;
• It must have suitable viscosity at remelting temperature.

Any inclusions in this molten metal are dissolved by and become

part of the slag, leaving a purified metal to pass as droplets through
the slag layer into the bottom of the mold.
45
• After the process has continued for some time, a purified
ingot having a controlled solidification structure is built up
in the mold.
• The slag, which also acts to prevent oxidation of the molten
metal in the usual case of operation in air atmosphere,
floats on top of the liquid metal at the top of the ingot due
to its relatively low density.

• Accordingly, the ESR ingot is free from macro-segregation

in spite of the large diameter and on the other hand the
cleanliness and homogeneity result in excellent mechanical
properties as compared to conventionally cast steel ingots.

46
• Process Variations
Three ESR process variations have been developed by
ALD:
• Remelting under increased pressure (PESR);
• Remelting under inert gas atmosphere (IESR);
• Remelting under reduced pressure (VAC-ESR).

47
 Pressurized / Vacuum Systems
(PESR)

48
http://web.ald-vt.de/cms/fileadmin/pdf/prospekte/esr_eng.pdf
 Features
•Melt-down in liquid slag created
by resistance heating
•Inert atmosphere
•Lowest sulfur content and
excellent cleanliness
•High yield
•Ingot diameter from 300 to 1600
mm
•Ingot weight from 2 to 160 t

49
https://www.sms-group.com/plants/all-plants/tertiary-metallurgy/
 Remelting under Inert Gas
Atmosphere (IESR)

50
http://web.ald-vt.de/cms/fileadmin/pdf/prospekte/esr_eng.pdf
 Electroslag Remelting under Vacuum
(VAC-ESR)

51
http://web.ald-vt.de/cms/fileadmin/pdf/prospekte/esr_eng.pdf
165 ton ESR ingot,
2,300 mm diameter x
5,000 mm long
52