18

Secondary Steelmaking
2 – Degassing

Topics to discuss ...

• Principles of degassing
• Degassing practices
 Principles of Degassing

• During steelmaking gases like oxygen, hydrogen and nitrogen

dissolve in steel.

• The term degassing is employed to remove nitrogen and hydrogen

from steel.

• Dissolved oxygen from steel melt cannot be removed as molecular

oxygen. Removal of oxygen is termed deoxidation.

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• Both nitrogen and hydrogen impair the mechanical properties of steel.

 nitrogen in liquid iron is 450 ppm and less than 10 ppm at room temperature
 excess nitrogen may form either blow holes or nitrides, which may causes
embrittlement of HAZ of welded steels and impair cold formability

• Hydrogen in steel impairs steel properties.

 solubility of hydrogen in steel is low at room temperature
 the excess hydrogen results in pinhole formation and porosity in steel
 few ppm of hydrogen causes blistering and loss of tensile ductility

• Thus removal of nitrogen and hydrogen from steel is necessary.

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 Thermodynamics of degassing reactions

Equilibrium relations of degassing reactions

Sl. No. Reaction Equilibrium relation Unit of h K vs. T relation Value at 1600°C
and 1 mm Hg

𝑗 alloy, i C Cr Ti P Si
log 𝑓𝐻 = 𝑒𝐻𝑖 %𝑖 + 𝑒𝐻 %𝑖 + ...
𝑒𝐻𝑖 0.045 0.005 -0.220 0.011 0.027
𝑗
log 𝑓𝑁 = 𝑒𝑁𝑖 %𝑖 + 𝑒𝑁 %𝑖 + ... 𝑒𝑁𝑖 0.130 -0.045 --- 0.051 0.047

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Problem
Calculate values of [H] when molten steel is degassed at 1850 K under vacuum.
The pressure above the melt is reduced in one case to 1 mm Hg and in other cases to 0.1 and
10 mm Hg. Steel contains C = 0.05%, Cr = 6%, Ti = 0.6%, Ni = 2%. Assume eNiH=0.

log fH = 0.045 x 0.05 + 6 x 0.005 + 0.6 x 0.22  fH = 0.795

log KH = -1905/T + 2.409  KH = 23.94

[ H ] f H  K H p1H/ 22  with the decreasing pressure above the melt dissolved

hydrogen in steel decreases
pressure (mm Hg) [ppm H]  higher degree of vacuum is beneficial to degassing
0.1 0.218  but higher degree of vacuum requires proper selection of
1.0 1.092 ladle refractory material to avoid decomposition of the
10.0 3.450 refractory
 also, side reactions may occur at higher degree of vacuum
• A pressure of 1 torr (= 1 mm Hg) in a • The [C] - [O] reaction is utilised for
vacuum chamber is thermodynamically removal of carbon to very low levels (ultra-
capable of lowering H, N and O to 2-3 low carbon steels) for special applications,
ppm levels. such as sheets for automobile bodies.

• This is in contrast to steels not treated
under vacuum, where the H and N
values can be as high as 5 ppm and 50
ppm, respectively.
• In actual degassing operations, removal
of hydrogen is fast and it often attains
equilibrium, but nitrogen removal is
more difficult because of slow kinetics.
• Besides the main reactions during vacuum
degassing, there are some minor side
reactions such as volatilisation,
decomposition of inclusions and melt-
refractory interactions. Some of these are:
(AlN) = [Al] + [N]
(CaO) = {Ca} + [O]
(MgO) = {Mg} + [O]
(MgO) + [C] = {Mg} + {CO}
(SiO2) + [C] = {Si} + 2{CO}
(SiO2) + [C] = {SiO} + {CO}
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Some general considerations

• The desorption of gases is a gas/ metal interfacial reaction.
 effectiveness of vacuum treatment increases with increase in surface area
of liquid exposed to vacuum
 increased surface area of molten steel exposed to vacuum
(e.g. treating liquid as thin stream or using gas induced stirring)

• Temperature of molten steel drops during vacuum treatment.

To compensate the heat loss, the following alternative may be considered.
 tapping of steel at a higher temperature, requiring increased energy in BOF/EAF
 additional heating during vacuum treatment
 the degassing time must be kept to minimum

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 Fluid flow in degassing

• Degassing can be carried out either [1] by placing ladle containing molten
steel under vacuum, or [2] by recirculation of molten steel in vacuum.

• In ladle degassing, the effectiveness of degassing decreases from top to

bottom of the molten steel bath.
 bottom layers of steel are less affected by vacuum since these layers are
under the influence of ferrostatic pressure due to column of liquid steel
 bath agitation helps exposing the entire content of molten steel to the vacuum
 argon bubbling during degassing leads to massive volumetric expansion of
bubbles at high temperature ( volume of gas becomes 6.3 times at 1873 K)
 moreover, rising gas bubbles absorb dissolved gases

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• In recirculation degassing argon is also bubbled through porous plugs

located at the bottom of the ladle.
 the speed of degassing increases with the increased rate of circulation (R)
of liquid steel through the vacuum chamber
 typically R ranges in between 10 – 100 ton/min
 circulation velocity increases with an increasing argon gas flow rate
 the rate of circulation R can be determined by
𝑃1
𝑅 = 7420 𝑄1/3 𝑑1/3 ln 𝑃2
R = circulation rate, kg/s
Q = argon gas injection rate, Nm3/min
d = internal diameter of leg, m
P1 = pressure at the base of downleg
P2 = pressure in vacuum chamber

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 Degassing Practices
• Degassing processes have been traditionally classified into the following
categories:
1) Ladle degassing processes (VD, VOD, VAD)
2) Stream degassing processes (ladle to ladle, ladle to mould)
3) Circulation degassing processes (batch (DH) and continuous (RH))

• Currently, stream degassing no longer exists. Ladle degassing processes

are widely used.

• Amongst the circulation degassing processes, DH is virtually non-existent,

while the RH (Ruhrstahl Heraus) process and its variants are the most
popular.

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 Ladle degassing
• Ladle containing molten steel is placed in a
chamber which is then evacuated.
• Ladles are generally lined with high alumina
bricks at upper part of the ladle while the lower
portion is lined with fireclay.
• After a determined time, ladle is removed from
the chamber and is teemed for casting.
• Ladle is provided with a porous plug at its bottom
to purge argon gas.
• The vacuum chamber is equipped with a hopper
so as to make additions of elements as and when
it is needed.
• Pressure is maintained in between 1 – 10 mm Hg
for effective degassing.
• In certain cases ladle is heated to compensate for
the loss of heat during degassing.
• For effective degassing of fully killed steel, argon is
purged through the bottom of the ladle.
• Stirring the bath enhances rate of gas removal.
Stirring gas is introduced either from top through the
roof by a submerged refractory tube or through the
porous plug fitted at the bottom of the ladle.
Electromagnetic stirring is also employed.
• Vigorous removal of gases causes metal splashing
too. Therefore ladle is not filled completely and
about 25% of its height is kept as freeboard to
accommodate the splashed metal droplets.
arrangement of ladle with porous plug
and hopper for degassing
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• During degassing, additions can also be
made for deoxidation and alloying.
• For the effectiveness of degassing,
BOF/EAF liquid should contain slag as low
as possible. Carry-over slag contains FeO
and since oxygen content of steel is in
equilibrium with FeO content of slag, oxygen
content of steel increases.
• The final content of gas in steel depends on
degree of vacuum and time of treatment.
Hydrogen is generally reduced to below
2ppm from 4 to 6ppm, nitrogen content of
steel is also reduced. The pick-up of nitrogen
from the atmospheric air may occur during
open pouring of steel, which must be
controlled.
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 sketch of a vacuum-argon-decarburisation (VAD) unit
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Stream degassing

• In stream degassing technology, molten steel is teemed into another

vessel which is under vacuum.

• Sudden exposure of molten stream in vacuum leads to very rapid

degassing due to increased surface area created by breakup of stream
into droplets.

• The major amount of degassing occurs during the fall of molten stream.

• Height of the pouring stream is an important design parameter.

• Has two variations: [1] ladle to mould, and [2] ladle to ladle

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1) Ladle to mould degassing

• Preheated mould with hot top is placed in vacuum

chamber.

• Above the chamber a tundish is placed.

• Steel tapped in the ladle at superheat equivalent

to 30°C is placed above the tundish.

• Steel is bottom poured in the tundish.

• One ingot could weigh around as high as 400

tons and several heats from different furnaces are arrangement of ladle, tundish and mould
used for casting. to degass molten steel

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2) Ladle to ladle degassing

• In ladle to ladle degassing, a ladle with the stopper rod

is placed in a vacuum chamber.

• Ladle containing molten steel from BOF or EAF is

placed on top of the vacuum chamber and the gap is
vacuum sealed.

• Stream is allowed to fall in the ladle where molten steel

is degassed.

• Metal stirring and ladle heating are not practical

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 Recirculation degassing
• In this method, molten steel is allowed to circulate in the
vacuum chamber continuously by special arrangement.
• In the RH process, molten steel is contained in the ladle.
• The two legs of the vacuum chamber (known as
snorkels) are immersed into the melt.
• Argon is injected into the upleg. Rising and expanding
argon bubbles provide pumping action and lift the liquid
into the vacuum chamber, where it disintegrates into fine
droplets, gets degassed and comes down through the
downleg snorkel, causing melt circulation. arrangement of cylindrical vessel and ladle
in RH degassing technology
• The entire vacuum chamber is refractory lined. There is
provision for argon injection from the bottom, heating, • circulation rate – 12 ton/min
alloy additions, sampling and sighting as well as video • argon requirement – 0.075 m3/min
display of the interior of the vacuum chamber. • heat loss – 20-50°C
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• In DH degassing process, a small amount 10-15% of the total mass of steel is

degassed at a time.

• The process is repeated until required level of degassing is achieved.

• The arrangement of a vessel and the ladle is somewhat similar to RH process

except the following:
 In DH unit, the cylindrical vessel has one snorkel
 Cylindrical vessel has heating facility, so that the DH degassing unit can operate with
lower superheats compared with RH unit
 The evacuated chamber is moved up and down so that steel enters the chamber.
The chamber is moved for 50-60 times with a cycle time of 20 seconds.
 A layer of slag is kept in the ladle to minimize heat losses.

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