Production of Stainless Steel: Part

Two
Sumrio:
For melting and refining of stainless steel grades there are many different
process routes. The individual choice is influenced by raw material availability,
desired final product, existing shop logistics and capital economics. In general
the stainless steelmaking process can be classified as a Duplex or Triplex type.
The Duplex refining process which is composed of electric arc furnace melting,
followed by converter refining, can be extended to a Triplex refining route by
installation of a VOD plant. Today, about 90% of all stainless steel is produced
according to the duplex or triplex route.
Slag Metal Reactions
For CaO-MgO-SiO2-(Fe, Cr) oxide slags with lime/silica ratios between 1.2 and 2.0, Pathy
and Ward found the experimental solubility limit of Cr2O3 in the slag to vary from 3% in
contact with low-chromium alloys (less than 2% Cr) to about 9% when the alloy was in the
range 14-20% Cr. These data agree with the phase diagram Cr2O3-CaO-SiO2 as determined
by Glasser and Osborn. These observations may have somewhat limited validity since it has
been found that the primary oxide phase is not Cr2O3, but, either chromite FeCr2O4 or Cr3O4.
In any case, it is a fact that commercial slags show substantially higher chromium oxide
solubilitys than indicated by these laboratory findings. The difference may also be due to
the solvent effect of alumina, iron oxide, and other components, the presence of
suspended solid oxides, or to the fact that slag and metal do not reach equilibrium in
commercial systems.
In laboratory studies by Pathy and Wird, a linear relation was found between the ratio of
chromium in slag to that in metal and the concentration of FeO in slag. The proportionality
constant varied from 0.5 at 2950F (1620C) to 0.3 at 3070F (1688C). In case of BOF
and EAF heats, Aukrust et al. obtained a value 0.28. For commercial operation the equation
(Cr)SLAG / [Cr]METAL = 0.3 (%FeO) .......... (1)
will give close representation of the chromium partition ratio. By measuring the iron oxide
concentration of the slag, the extent of chromium oxidation can be determined. The degree
of oxidation of the slag depends on practice and must be determined experimentally.
There are many different process routes for melting and refining of stainless steel grades.
The individual choice is influenced by raw material availability, desired final product,
existing shop logistics and capital economics. In general the stainless steelmaking process
can be classified as a Duplex or Triplex type. The Duplex refining process which is
composed of electric arc furnace melting, followed by converter refining, can be extended
to a Triplex refining route by installation of a VOD plant. This is necessary, if very low
carbon, sulfur or nitrogen contents must be achieved in the final product. Today, about
90% of all stainless steel is produced according to the duplex or triplex route.
In Duplex process, after melting in primary unit, refining is carried out in different vessel.
Duplex process have certain disadvantages with respect to the ratio of ferro-alloys to scrap
in the case of VOD and higher argon, ferro-silicon consumption and shorter converter life in
case of AOD, lengthy process time in secondary vessel converter. However, in order to
overcome these demerits and produce different grades with grater economy and better
quality, triplex process is used.
In Triplex process, after melting in primary unit, refining is carried out in two different
vessels. In the first vessel, decarburization and major refining take place and final stages of
desulphurization and degassing take place in second vessel.
Compare to duplex, triplex process has following merits:
Increase productivity
Increase number of heats per day
Increase scrap to liquid metal yield
Improved quality of metal
High operational flexibility
Comparatively lower cost of production.

Figure 1: The standard process routes for stainless steels
AOD process
The AOD process features the use of mixed gas (O2 + inert gas) top-blowing lances to
achieve high decarburization rates even at low steel bath [C] contents. The AOD (argon-
oxygen decarburization) is a bottom-blown process, which since its introduction in the late
1960s has become the dominant stainless steelmaking process (Figure 2). The AOD is
charged with molten steel. The main task in the AOD is to refine crude steel high in both
carbon and sulfide. The often-high carbon content is oxidized and driven off as carbon
monoxide when oxygen is blown through tuyeres located near the bottom.

Figure 2: Schematic AOD Converter
Chromium oxidation is inevitable in the oxygen blowing decarburization process and
chromium oxide with its high melting point is enriched in the slag at steel-making
temperature. Depending on carbon and sulfur demands in the product, the top slag is
reduced with either ferrosilicon or aluminum or a combination of both.
Ferrosilicon is used when sulfur levels only needs to be lowered slightly or when the sulfur
already is low enough. Whenever possible, ferrosilicon is used because it is less expensive.
Low sulfur levels as well as low carbon are achievable in the AOD converter.
Decarburization in AOD converter
Very low carbon levels are acquired in AOD stainless steels, often down to between 0.01
and 0.04 percent. The concept of the AOD converter is reaching such low carbon content
by introducing increasing amounts of argon into the oxygen blown through the steel bath
in the decarburization step. The argon dilutes the carbon monoxide formed during the
decarburization, which lead to a lower the partial pressure of carbon monoxide PCO.
A low carbon monoxide partial pressure favors the formation of carbon monoxide from
carbon and oxygen according to the oxygen potential diagram and therefore a lower
temperature can be implemented in the AOD converter in making a standard stainless steel
with chromium content of 18% and carbon level at 0.03% (Figure 3). At normal pressure
(1 atm) a temperature of 1940C is required to reach such a low carbon level. When the
partial pressure of carbon monoxide PCO is reduced to a tenth of normal atmospheric
pressure the equal low carbon level can be met already at 1600C (Figure 3). Economical
benefits are shorter heating times and lower heating costs combined with less refractory
wear, and perhaps less expensive refractory not needing to withstand extreme
temperatures.

Figure 3: Oxygen potential diagrams
The efficiency of carbon removal is described in terms of the percentage of total inserted
oxygen that is consumed in the oxidation of carbon. This Carbon Removal Efficiency (CRE)
is described in equation 2. The rest of the oxygen is occupied in oxidizing metal. Keeping
the CRE high is therefore of great importance.
CRE = O2(carbon oxidation) / O2(total) x 100 (%) .......... (2)
When the CRE decreases it indicates the necessity to decrease the oxygen to argon ratio,
i.e. higher argon content in the blowing gas is needed. The blowing is therefore performed
step by step constantly increasing the argon content in the gas.
Figure 4 shows schematically a decarburization procedure. In the initial step the CRE
reaches 90%. The efficiency of carbon decrease as the available carbon in the melt
lessens. Step two with equal amounts of oxygen and argon in the blowing gas, starts when
CRE is approximately 45% and carbon level is 0.44%. CRE rises to 100%. All oxygen is
consumed in forming carbon monoxide. After a few minutes CRE decreases again along
with the carbon level. Step three is acting in the same manner but with even higher argon
content. The blowing is performed until the requested carbon level is met. It may require a
fourth step with 100% pure argon blown through the melt.

Figure 4: Chrome Reduction Efficiency CRE in AOD convertor
Not only carbon will be removed during the decarburization procedure, but also other
elements with high affinity to oxygen such as silicon, manganese, chromium and nickel.
Stainless steel is highly alloyed with chromium and nickel. Chromium and nickel, as well as
iron, will inevitable at some extent are oxidized during the decarburization.
A major loss of valuable chromium to the slag in the form of oxides is not acceptable. Due
to the argon dilution carbon is oxidized prior to chromium. The reaction written:
[C] + [O] (CO) .......... (3)
4[Cr] + 3(O2)(G) 2Cr2O3(S) .......... (4)
Cr2O3S + 3[C]Fe 2Cr + 3CO(G) .......... (5)
With the overall reaction of these two combined
2[Cr] + 3CO(G) Cr2O3(S) + 3[C] .......... (6)
Interestingly enough equation 6 does not reach equilibrium according to laboratory and
plant studies. The studies indicate that chromium oxidation occur at greater extent than
expected at a certain carbon level and a certain oxygen/argon ratio. Fulton and
Ramachandran showed that chromium oxidation depends of blowing procedures. The
argon protection against chromium oxidation is diminished if the gas is blown only shallow
into the melt from a lance above. The oxygen is consumed in instant chromium oxidation
equation 7 instead of forming carbon monoxide.
4[Cr] + 3O2(G) 2Cr2O3(S) .......... (7)
If the gas mixture on the other hand is injected through tuyeres placed near the bottom of
the converter the solid chromium oxide particles formed by the instant oxidation come to
better use. As the formed Cr2O3particles ascend to the surface they perform the actual
decarburization. The Cr2O3 particle come in the contact with carbon on its way up and as a
result are freed from one or more of its oxygen, hence leading to the formation of carbon
result are freed from one or more of its oxygen, hence leading to the formation of carbon
monoxide. The reactions can be written as
Cr2O3(S) + 3[Cr]Fe 2[Cr]Fe + 3CO(G) .......... (8)
Chromium oxide particles totally freed from their oxygen molecules re-emerges again as
chrome in the melt. Those Cr2O3 particles not subjected to any carbon on their path ends
up in the slag, explaining the existence of chromium oxide in the slag despite of equation
11. Chromium content in the top-slag is often referred to as only Cr2O3 even though some
extent of it is CrO.
In slag chrome is present both as Cr2O3 and CrO. The formation of CrO is favored by
increased temperature, decreased oxygen potential and decreased basicity. In order to
keep the chromium trivalent, remaining as Cr2O3 the basicity should be held high.
Large amounts of argon purge the steel bath intensely. Nitrogen and Hydrogen follow the
argon to the surface and very low levels remain in the steel at the end of the process.