16

Stainless Steelmaking

Topics to discuss ...

• Introduction
• Thermodynamics of decarburization of chromium melt
• Technology of stainless steel making
 Introduction
• Stainless steels contain typically 10-30 %
chromium besides other elements like C,
Mn, Si, S etc.
• Types of stainless steels:
 Austenitic stainless steels:
Cr = 18%, Ni = 8%, C = 0.03-0.15%

• Chromium imparts corrosion resistance to  Ferritic stainless steels:

Cr = 12-30%, C = 0.08-0.12%
steel.
 Martensitic stainless steels:
• Varying amounts of other alloying elements Cr = 13%, C = 0.15-0.25%
like Ni, Mo, V, Ti, Ni, etc may be added to  Duplex stainless steels:
obtain certain specific property. Cr ~ 25%

It may be noted that all stainless steels
contain chromium and carbon besides other
elements. Production of stainless steels
requires controlling chromium and carbon.
 Precipitation hardenable stainless steel:
Cr = 18-20%,Ni = 8-10 % Ni and Cu, Ti, Al
3/17

Thermodynamics of Decarburization
of Chromium Melt

• In stainless steel making, both chromium and carbon oxidizes when

decarburization of melt is done.
 so the central problem is to achieve enough oxidation to bring the carbon
content down to 0.03% without excessive loss of chromium

• The Ellingham diagram for oxide formation indicates that carbon

oxidation in preference to chromium oxidation can occur at temperatures
greater than 1220 °C, when both elements are in pure state.

• Under all practical conditions, however, carbon oxidation can occur at

temperatures above 1800 °C in presence of chromium.
4/17
 2C + O2 = 2CO • Hilly and Kaveney proposed the following
equation for distribution of Cr and C:
2Cr + 1.5 O2 = Cr2O3 or
3Cr + 2O2 = Cr3O4 [𝐶𝑟] 13800
log =− + 8.76 − 0.925 log 𝑝𝐶𝑂
[𝐶] 𝑇
• Equilibrium distribution between Cr and
C is represented by considering Cr3O4
(Cr3O4) + 4[C] = 3[C]r + 4{CO}
• The effect of Ni
[𝐶𝑟] 13800
log =− + 8.76
• Assuming pure Cr3O4 and using Henry’s [𝐶] 𝑇 + 4.21[𝑁𝑖]
law for carbon and chromium, it follows −0.925 log 𝑝𝐶𝑂
𝑓𝐶𝑟 3 [𝐶𝑟]3 𝑝𝐶𝑂 4
𝐾=
𝑓𝐶 4 [𝐶]4
• The above two equations describe distribution
[𝐶𝑟]3 𝐾 x 𝑓𝐶 4
= ratio of Cr and C in Fe-Ni-Cr-C melt.
[𝐶]4 𝑓𝐶𝑟 3 𝑝𝐶𝑂 4

fC and fCr are activity coefficient of C and

Cr in liquid iron at 1wt % standard state.
5/17

lowering of pco allows the

same to be achieved at a
much lower temperature

very high temp. needed

if C is decreased <0.04%
with high Cr content

Chromium-carbon-temperature relationship Influence of pressure and temperature on the retention of

in oxygen saturated steel melts (pCO = 1 atm) chromium by oxygen saturated steel melts at 0.05% C
6/17
• Table showing the influence of temperature and pCO on the distribution
ratio R = [Cr]/[C] without Ni and R1 = [Cr]/[C] in the presence of 10% Ni.

Table: chromium / carbon distribution ratio

pCO = 1 atm pCO = 0.25 atm pCO = 0.10 atm

T (K)
R R1 R R1 R R1
1873 25 36 89 129 207 301
1973 55 82 209 295 488 690
2073 128 173 460 619 1077 1477
2173 240 339 863 1220 2019 2852

We can infer the following form the table:

a) Increasing temperature increases R and R1 at all pCO .
High temperature is required to suppress Cr oxidation in favor of C oxidation
b) Decreasing pCO increases R and R1 at all temperatures
c) Nickel increases R and R1
7/17

• The above observations suggest that

 high temperature is needed to remove carbon in presence of

chromium, if stainless steel is produced at atmospheric pressure.

 If reduced pressures are used, lower temperature can cause

oxidation of carbon.

8/17
 • For the reduction of chromium oxide from slag by ferrosilicon
during the last stages of VOD/AOD operation, Hilty et al. assumed
the following reaction
3 2
ℎ𝐶𝑟 𝑎𝑆𝑖𝑂2
(Cr2O3) + 2[Si] = 3[Cr] + 2(SiO2) ; 𝐾= 2
ℎ𝑆𝑖 𝑎𝐶𝑟2𝑂3

• Noting that activities of SiO2 and Cr2O3 in slag are functions of slag
basicity, equilibrium relation can be arrived at from the equation for K.

• However, for practical purposes, statistically fitted empirical coefficients

are recommended, such as:
log [Cr]slag = 1.283 log [Cr] – 0.748 log [Si] – 1.709 log V – 0.923
where V = slag basicity = (CaO + MgO)/SiO2

9/17

Technology of Stainless Steelmaking

• Stainless steel can be produced by two routes:

1) electric arc furnace (EAF) route

2) electric arc furnace plus argon oxygen decarburiser (EAF + AOD) route,
commonly known as the duplex process.

• There is another process, called triplex refining, where electric arc furnace
melting and converter refining are followed by refining in a vacuum system, is
often desirable when the final product requires very low carbon and nitrogen
levels. This third step makes the cycle time even longer and adds to cost.

10/17
 EAF Route
• Electric arc furnace was used to produce stainless steel by melting scrap
of the desired composition. EAF was used only as a melting unit.

• Typically, charge consists of

 stainless steel scrap
 carbon steel scrap
 reduction slag mix (FeSi - FeCrSi - CaO - Al) containing low carbon
 low carbon FeMn and FeCr

Ferrochrome, containing ~55 - 70% Cr is the principal source of chromium.

Classification of FeCr based primarily on their carbon content, such as:
• Low carbon ferrochrome (about 0.1% C) – most expensive
• Intermediate carbon ferrochrome (about 2% C)
• High carbon ferrochrome (around 7% C) – least expensive
11/17

• The scrap is melted in EAF and after
melt-down period, the melt contains
around 10% Cr, all Nickel and carbon.
Melt consists of Fe-Cr-Ni-C alloy.
• At low temperature, Cr is protected by
ensuring sufficient Si in the melt.
• The blow is discontinued when carbon level
is below specification.
• In spite of high temperature, the slag
contains about 50% Cr2O3. To recover Cr
from slag, the reduction slag mix is added
[ 2Cr2O3 + 3Si = 3SiO2 + 2Cr ].

• Oxygen is blown onto the melt and the • After 5-10 minutes reaction time, low carbon
temperature is raised quickly to about coolants (SS scrap) are added to bring the
2000 °C. temperature down to about 1600 °C.

• Initially chromium oxidizes until bath
temperature rises to 1800 °C. Carbon
oxidation occurs at the expense of
chromium once the bath temperature
rises to 1800 °C.
• In the finishing stage, low carbon
ferrochrome is added to make the chromium
content of steel to a desired value.
12/17
• The disadvantages with this technology are
 Slow process (tap-to-tap time = 5-6 hours)
 High temperature is required which cause damage to the refectory lining.
 Low carbon ferrochrome is required which in expensive
 Low Cr yeild (~87%)

• Thus a technology which can use high carbon ferro-chrome and to decarburize
the bath at selectively lower temperatures would be required.

• If carbon is to be oxidized in preference to Cr at low temperatures, a reduction

in low CO pressure would be required.

• This can be achieved either by vacuum or by diluting the oxygen gas by adding
argon gas. The former one is vacuum oxygen decarburisation (VOD) and the
later is argon oxygen decarburisation (AOD).
13/17

EAF + AOD Route

• The process in carried out in a converter type of vessel,

lined with magnesite brick.

• A mixture of argon + oxygen gas is injected through the tuyeres

located on the side of the converter shell.

• Fe-Cr- Ni-C alloy melt is prepared in EAF.

• The unrefined melt is charged in AOD vessel. High carbon-ferrochrome is charged.

• In the initial stage a mixture of O2: Ar in 3:1 ratio is blown through the side tuyeres.

• When carbon reduces to 30% of the original value the ratio of O2: Ar is changed to
2:1 (as Cr needs more protection). Blow continued until C reduced to 0.09-0.12%.
14/17
• First stage of blow generates sufficient amount of heat due to oxidation of
Si, C, and small quantities of Cr, Mn and Fe. Coolants (SS steels scrap,
pure Ni, other alloys if needed) are added (5% of the change) at several
points to avoid excessive damage of the refractory lining.

• In the final stage, the ratio of O2:Ar is changed 1:3 to bring C to the desired
value. Fe- Si is added to recover Cr from slag and slag basicity is
maintained at 1.5 - 2 by adding a reduction slag mix (CaO+FeSi).

• Slag formation and slag metal reactions are facilitated by argon stirring of
the bath. The bath is desulphurized to levels well below 0.015% in a few
minutes by preparing a new slag (CaO+FeSi+CaF2).

15/17

AOD vessel

Illustration of duplex and triplex methods of stainless steelmaking

16/17
• Advantage of EAF+AOD Process

 Process yield for Cr is ~93% (EAF+AOD), ~97-99% in AOD vessel.

 High carbon ferroalloys can be used.
 Cycle time of AOD is roughly matches EAF (2-2.5 hrs). Thus, the use of AOD
can roughly double the stainless steel production from one EAF.
 Mixing is violent during AOD process, producing cleaner steel with low
dissolved gas.
 Very low C and S level can be obtained.

17/17