03 - Iron and Steel Making

Materials engineering
Iron and steel

making
Metals: rarely exist in pure state  mostly in ores
Ore: Metallic and other compounds,

mostly oxides
Metallic content:
Iron ores: 30-70% Fe
Copper ores: 0.1-0.8 % Cu
Molybdenum: 0.01-0.1% Mo
4 basic way to gain the metallic parts from ore:

Reduction by carbon
Electrolytic way
costs
Metallotermical process
Dissociation
1) Reduction by carbon MeO + C  Me + CO
FeO + C  [Fe] + {CO}
molten metals gas
2) Electrolytic way Al2O3  Al23+ + 3O2-

on the cathode: Al3+ + 3e-  Al
3) Metallothermical process
TilCl4 + 2Mg [Ti] + 2MgCl
4) Dissociation MeX  [Me] + [x]

only at high energy level
Iron and steel
Iron and steel making
Blast furnace
Foundry
Steel making
plant
Foundry
Production of molten steel
Iron producing processes
Purpose: Iron ore  Pig Iron
ore types: Fe3O4 magnetite ~70% Fe

Fe2O3 hematite ~70% Fe
FeCO3 siderite ~50% Fe
+ tailings: silicates, sand, other non ferrous

MnO, Al2O3, P2O5, etc
Concentration of ore
cost cost of pig iron

cost of concent-
rating
cost of blast
furnace
30 ~ 70 % Fe % in ore magnetite
Blast Furnace Plant
Blast Furnace Plant
Tasks
1) Reduction of the ore
2) Extraction of tailings
3) Melting  separation of the molten iron from the
molten tailings (spec. weight difference)
Charge: Ore + Coke + Limestone
Dimension of the BF: For 1000 t of iron:

Diameter: 4-10 m 2000 t ore +
Height: 25-30 m 800 t coke +
Volume: 300 – 5000 m3 500 t limestone +
~ 4000t hot air
Processes in blast furnace
Charge moves down (6-8 hours)
- Preheating by gas: coke burns more efficient

Formation of CO
CO reacts with iron ore
- Coke reduces CO2 in the gas
C + CO2  2CO
- CO reduces the surface of the iron ore. Indirect reduction
FeO + CO  Fe + CO2
- Slag producing by limestone.
CaCO3  CaO + CO2
MgCO3  MgO + CO2
- In the bosh the coke burns
C + O2  CO2 + Heat
- The coke reduces the molten ore. Direct reduction
FeO + C  Fe + CO
- Molten limestone + other slag components produce eutectic slag
Slag floats over molten iron
Processes in blast furnace – thermodynamics
• Gibbs free energy

• Reduction of FeO from
690 °C
C+O2CO2
Carbon reduces the oxides:

FeO + C  Fe + CO
MnO + C  Mn + CO alloying elements

SiO2 + 2C  Si + 2CO
P2O5 + 5C  2P + 5CO impurities

SO2 + 2C  S + 2CO
in molten iron gas
In BF carbon can reduce S, P, Cr, Mn, Si 70-90%

and Ti 10-20%
Sulfur and phosphorous are harmful in pig iron, and they must be
removed.
Desulfurization
FeS + CaO  FeO + CaS
in molten iron in molten slag
Dephosphorization
P2O5 + 5FeO + 5C + 4 CaO  CaO4P2O5 + 5Fe + 5CO
in molten iron
in molten slag gas
in molten iron
Result: pig iron

Product of blast furnace
At the bottom of the BF:

Slag on the top
Molten iron on the bottom with~4% C
Near to eutectic composition
Taping at different heights:

different composition different
purpose
C% Mn% Si% S% P%
for casting 3-4 <1 <4 < 0.1 < 0.1
for steel with Bessemer method 3-4 0.4 – 1 ~3 < 0.1 < 0.1
for steel with Thomas method 3-4 0.4 – 1 ~2 < 0.1 < 0.1
for steel with Siemens-Martin
3-4 0.4 – 1 ~1 < 0.1 < 0.1
method
Taping:
http://www.youtube.com/watch?v=QBLRIEZZEsU
Metallurgy
http://www.youtube.com/watch?v=kPH4dJUVOfc
Steel making
Purpose Pig iron  steel by fire – refining treatments that

decrease the C content and impurities.
Main steps
1) Charging
2) Oxidation decreasing C content
3) Increasing temp. with decreasing C% the Tmelt increases !
4) Deoxidation decrease FeO and O in molten steel
5) Alloying
6) Casting, solidification
casting of ingots or
continuous casting of bars and billets
Steel making
Processes
 Siemens Martin (open hearth furnace)
 Bessemer converter process
 Thomas converter process
 Oxygen converter process (Linz-Donawitz process - LD)
 Electric arc steel furnace
Siemens Martin process (1864)
Charging
pig iron+scrap
pig iron + ore
Capacity
10-900 t
6-12 h
Too expensive
carbon
0,3 %/hour
burns out
Siemens Martin process (1864)
Bessemer process (1856)
Charging
molten iron
1210-1250ºC
~3% Si
Capacity
5-60 t
15-20 min
First converter method

No external heat
Acidic lining (slag
react.)
Si + O2  SiO2
from the air

Bessemer process (1856)
During the blow C, Si, Mn % decreases.
% ºC 1700ºC
1250ºC
C
Si O
4%
3%
Mn
1% N
blowing time
15 min.
Thomas converter process (1878)
Charging
molten iron
1210-1250ºC
~2% P
No external heat
Similar to Bessemer, but basic lining for slag reaction.
4 P +5 O2  2 P2O5
from the air

Oxygen-converter process (LD)
Charging
molten iron
~3% C
~0.5% Mn
~1% Si
~0.1% P, S
Capacity
15-400 t
No external heat
To avoid overheating when blowing iron ore or scrap are changed.

Limestone is changed for desulfurization & dephosphorization.
Variants of Oxygen-converter process
OLP process
oxygen – limestone – powder
oxygen & CaO powder is blown through the lance
AOD process
argon – oxygen – decarbonizing

oxygen & argon is blown through the lance
Mixed gas system  decreased partial pressure of oxygen

 C% decreases
up to 0.002% C e.g. for stainless steels

Electric Arc Steel Furnace
Charging
scrap + solid pig iron
~3% C
~0.5% Mn
~1% Si
~0.1% P, S
Capacity
5-200 t
For high grade steels
T > 2500ºC intensive reaction, N2 dissociation

http://www.youtube.com/watch?v=nolpiat6Sk0
Charging scrap
http://www.youtube.com/watch?v=G6Uxh-xtU-g
during work
http://www.youtube.com/watch?v=3gg9_zTlg4M
Electrode in the furnace

Steel making - oxidization
Purpose decrease C% and oxidize the impurities (S, P)
In open hearth and electric arc furnace
C + FeO  Fe + CO
from scrap turbulence in the charge

or iron ore
In air or oxygene blowing converters
2C + O2  2CO
from blowing The dissolved oxygen content

air increases
Hamilton’s law
At the given temperature [C][O]=constant
O%
Stainless steels oxidization
requires vacuum
0.1 C < 0.02%
O < 0.01%
0.01 p=1bar
0.001
0.0001 p=1mbar
0.01 0.1 1 C%
The law of distribution and mass action
The law of distribution

At a given temperature the ratio of the amount of a given compound
In the molten iron and in the molten slag is constant.
𝐹𝑒𝑆𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔

𝐿(𝑇) =
𝐹𝑒𝑆𝑖𝑛 𝑡ℎ𝑒 𝑖𝑟𝑜𝑛
The law of mass action

Determines the direction of the reaction
v1
mA + nB v2 pAB
v1=k1(CAB)p V2=k2(CA)m(CB)n
At equilibrium v1=v2
Effect of nonmetallic elements S, P, O, N
Effect of sulfur FeS at grain boundaries
S does not dissolve, forms FeS eutectic with iron.

grain
T
Crystallization at the grain 1600
boundaries.
1000
Cold and hot brittleness
FeS %
0% ~80% 100%
To reduce the effect: desulfurization
1) Alloy with Mn 2) Increase S content
FeS + Mn  MnS + Fe generally S < 0.035%
MnS is formable at
high temperature
Effect of sulfur - desulfurization
𝐹𝑒𝑂𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔

𝐿= increases with temperature
𝐹𝑒𝑂𝑖𝑛 𝑡ℎ𝑒 𝑖𝑟𝑜𝑛
𝐶𝑎𝑆𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔 ∙ 𝐹𝑒𝑂𝑖𝑛 𝑡ℎ𝑒 𝑖𝑟𝑜𝑛 𝐶𝑎𝑆𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔 ∙ 𝐹𝑒𝑂𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔
𝐾= =
𝐹𝑒𝑆𝑖𝑛 𝑡ℎ𝑒 𝑖𝑟𝑜𝑛 ∙ 𝐶𝑎𝑂𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔 𝐹𝑒𝑆𝑖𝑛 𝑡ℎ𝑒 𝑖𝑟𝑜𝑛 ∙ 𝐶𝑎𝑂𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔 ∙ 𝐿
𝐶𝑎𝑆𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔 ∙ 𝐹𝑒𝑂𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔

𝐹𝑒𝑆𝑖𝑛 𝑡ℎ𝑒 𝑖𝑟𝑜𝑛 =
𝐾 ∙ 𝐶𝑎𝑂𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔 ∙ 𝐿
To achieve low S%
• increase L : increase the temperature.
• increase CaO content in the slag
The slag must be
• increase CaS content in the slag changed
• increase FeO content in the slag
Effect of nitrogen
nitride compounds precipitation

and/or the solidification of nitrogen in
interstitial solid solution.
 Increases strength decreases

toughness.
 Ageing
Effect of phosphorous
T
Keep P content under 0.035%
(0.001%) γ
α
1000
1.2% 15%
Impact energy Rm Rm
Rp02
Z Rp02
Z
T
TTKV TTKV
P [%]
P% ↑
Effect of phosphorous - dephosphorization
2 P + 5 FeO + 4 CaO  (CaO4 · P2O5) + Fe

in molten iron
in molten iron in molten slag
Dissolves only in slag
[𝐶𝑎𝑂4 · 𝑃2𝑂5] ∙ [𝐹𝑒] 5 [𝐶𝑎𝑂4 · 𝑃2𝑂5] ∙ [𝐹𝑒]5

𝐾= [𝑃] =
𝑃 2 𝐹𝑒𝑂 5[𝐶𝑎𝑂]4 𝐾 𝐹𝑒𝑂 5[𝐶𝑎𝑂]4
To achieve low P%
• decrease the temperature.
• increase CaO content in the slag
• increase phosphate content in the slag The slag must be
changed
• increase FeO content in the slag
stress after long service period
Effect of oxygen
after forming
In form of O or FeO.
initial state
Ageing
strain
Work done till fracture

Impact energy
To reduce the effect: deoxidation
Methods:
 Settling
 Diffusional deox.
T
TTKV TTKV  Synthetic slag
O% ↑  Ladle metallurgy
Brittel-to-ductile transition temperature
Effect of oxigene
Rm
Z
Rm
O [%]
Deoxidation: settling
Deoxidizing elements are loaded into the molten steel.

General reaction:
FeO + Me  MeO + Fe
The amount of deoxidizing elements are limited by their

disadvantageous effect on the properties:
Mn < 1% causes grain coarsening & brittleness

Si < 0.5 % it decreases the toughness.
V
Ti < 0.1 % they decreases the toughness.
Al
Effect of deoxidizing element on the dissolved oxygen
O [%]
0.1 Mn
Si
0.01 V C
0.001 Al
Ti
0.0001
Zr
Me [%]
0.01 0.1 1
Rimmed steel Deoxidizing with Mn only

susceptible on ageing
Semi-killed steel Deoxidizing with Mn + Al

for continuous casting
Killed steel Deoxidizing with Mn + Si

lower TTKV than rimmed steel
Dead killed steel Deoxidizing with Mn + Si + Al/V/Ti/Zr

best quality from the point of brittleness
Deoxidation: diffusional and synthetic slag meth.
Diffusional method
Deoxidizing element loaded on the top of the molten

slag. Diffusion of O to slag.
Diffusional synthetic slag method
The molten steel is poured on the top of prepared

FeO-free slag.
molten steel
FeO free slag

Deoxidation: ladle metallurgy
Ladle metallurgy
Powder injection
deoxidizing, desulfurizing, and dephosphorising
powder with Ar gas are blown into the molten
steel.
- Inclusions are lifting to

the slag. molten steel
- Almost isotropic
This technology with the converter method is the most up-to-date steel
making process
Vacuum handling
A process for deoxidation and degasification
The effect of vacuum on steel

1) Decreasing the partial pressure of the gas above the
molten steel
2) Decrease the content of oxygen.
3) Increase the vaporization rate of low melting point
metals (Zn, Pn, Sn, As)
4) Separates the compounds by dissociation.
~10-6 bar ~10-9 bar 10-12-15 bar
Practically
Fe4N FeO SiO2 impossible
CrN AlN Al2O3
TiN
Vacuum handling
Two type of process
Molten steel
Vacuum
Vacuum chamber
Steel stream
ladle
Degasificated
steel
Vacuum ladle degassing Vacuum stream degassing

Effect of dissolved gases on steel
CO - in the rimmed steel produces gas bubbles
O2 - produces gas inclusions and oxide and silicate

inclusions
N2 - increase the ability for aging and nitride inclusions
H2 - flocking – H2 bubbles  cracking

Tmelting
flocking – H2 bubbles
reason
A4
[H]
[H]
A3
Temp
A3 A4 Tmelting
H2 – solution
let the gas atoms depart by diffusion
• slow cooling after casting (several days)

• forging by very soft deformation to make cohesion between
the surfaces of the cracks
+ for N make stable nitrides my mircoalloying elements
Al, V, Ti  AlN, VN …
Alloying, casting
Alloying
Can only take place after a perfect deoxidation, otherwise

alloying elements would burn.
Casting
Two types: casting of ingots continuous casting

Casting of ingots
• simple • More homogeneous

• High productivity • slow
Casting of ingots
Solidification process for ingots

- Shrinking effect
- Crystallisation, grain-arrangement, mircostructure
- Segregation
Casting of ingots
Shrinking effect
the top 12-15% of the total weight of killed

steel ingot must be cut off (rimmed steel only
3-5%)
Casting of ingots
Crystallisation, grain-arrangement, mircostructure

R – rate of crystall growing
R
N N – number of
crystal nuclei
ΔT Supercooling –
under the
equilibrium
Casting of ingots
Segregation – normal segregation
During the solidification the liquid phase becomes enriched

with alloying elements and impurities.
R – rate of crystall growing

T
The difference can be
300% for S
P% 500-600% for P
S%
C%
Concentration of the
liquid phase
cross section of the ingot
B [%]
Casting of ingots
dendrite
Segregation – inverse segregation
Because shrinkage the alloying elements

and impurities can move inwards between
dendrites.
liquid
phase
The impuritiy concentration is higher Concentration %

between the dendrites’ arm.
Casting of ingots
Microstricture and segragation in ingot
http://www.substech.com/
Casting of ingots
Continuous casting
Continuous casting
• https://www.youtube.com/watch?v=d-
72gc6I-_E
Steel refining methods
All of these methods have a remelting and solidification period to:
- Decrease the dissolved gas content and the amount of inclusions

- Produce a homogeneous fine grained crystal structure
- Produce a homogeneous distribution of alloying elements
Used for
- tool steels
- high alloy steels
Vacuum arc remelting process
 Removal of dissolved gases, such

as hydrogen, nitrogen and CO;
 Reduction of undesired trace
elements with high vapor pressure;
 Improvement of oxide cleanliness;
 Achievement of directional
solidification of the ingot from
bottom to top, thus avoiding
macro-segregation and reducing
micro-segregation.
Vacuum induction remelting process
 Removal of undesired trace elements with high vapor pressures
 Removal of dissolved gases (hydrogen and nitrogen)

Electroslag remelting process
Similar technology:
electron beam
remelting process

03 - Iron and Steel Making

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03 - Iron and Steel Making

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Materials engineering

Iron and steel

Ore: Metallic and other compounds,

4 basic way to gain the metallic parts from ore:

molten metals gas

2) Electrolytic way Al2O3  Al23+ + 3O2-

4) Dissociation MeX  [Me] + [x]

Purpose: Iron ore  Pig Iron

ore types: Fe3O4 magnetite ~70% Fe

+ tailings: silicates, sand, other non ferrous

cost cost of pig iron

Charge: Ore + Coke + Limestone

Dimension of the BF: For 1000 t of iron:

Charge moves down (6-8 hours)

- Preheating by gas: coke burns more efficient

• Gibbs free energy

Carbon reduces the oxides:

MnO + C  Mn + CO alloying elements

P2O5 + 5C  2P + 5CO impurities

in molten iron gas

In BF carbon can reduce S, P, Cr, Mn, Si 70-90%

in molten iron in molten slag

Result: pig iron

At the bottom of the BF:

Taping at different heights:

Purpose Pig iron  steel by fire – refining treatments that

First converter method

from the air

During the blow C, Si, Mn % decreases.

Similar to Bessemer, but basic lining for slag reaction.

from the air

To avoid overheating when blowing iron ore or scrap are changed.

oxygen – limestone – powder

oxygen & CaO powder is blown through the lance

argon – oxygen – decarbonizing

Mixed gas system  decreased partial pressure of oxygen

up to 0.002% C e.g. for stainless steels

For high grade steels

T > 2500ºC intensive reaction, N2 dissociation

Electrode in the furnace

Purpose decrease C% and oxidize the impurities (S, P)

In open hearth and electric arc furnace

from scrap turbulence in the charge

In air or oxygene blowing converters

from blowing The dissolved oxygen content

At the given temperature [C][O]=constant

The law of distribution

𝐹𝑒𝑆𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔

The law of mass action

Effect of sulfur FeS at grain boundaries

S does not dissolve, forms FeS eutectic with iron.

1) Alloy with Mn 2) Increase S content

FeS + Mn  MnS + Fe generally S < 0.035%

Effect of sulfur - desulfurization

𝐹𝑒𝑂𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔

𝐶𝑎𝑆𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔 ∙ 𝐹𝑒𝑂𝑖𝑛 𝑡ℎ𝑒 𝑠𝑙𝑎𝑔

nitride compounds precipitation

 Increases strength decreases

Effect of phosphorous - dephosphorization

2 P + 5 FeO + 4 CaO  (CaO4 · P2O5) + Fe

[𝐶𝑎𝑂4 · 𝑃2𝑂5] ∙ [𝐹𝑒] 5 [𝐶𝑎𝑂4 · 𝑃2𝑂5] ∙ [𝐹𝑒]5

Work done till fracture

Deoxidizing elements are loaded into the molten steel.