Thermodynamic and kinetic aspects of

secondary steelmaking processes

K. W. Lange

(decarburisation, dephosphorisation) and reducing

The introduction of secondary steelmaking has (desulphurisation, deoxidation) reactions. Nowadays
been one of the most significant developments in nearly all steel shops use the primary furnaces only
steelmaking in recent decades. In this review the for melting and rough compositional control, the
operations, reactions, and reactors of secondary final adjustment being made in the ladle.
steelmaking are discussed in an attempt to Ladle metallurgy offers a variety of methods,
explain the objectives, mechanisms, benefits, and
differing in their metallurgical possibilities. Many
potentialities of the processes by rigorous
combinations of the extensive range of process
application of thermodynamic and kinetic
principles. It is thought that by this means a
variables may be applied, allowing an optimum
deeper understanding might develop on what adaptation to achieve technical and economic
occurs in the reactors and how steelmaking can objectives. Some of the physical possibilities are
be achieved at the lowest cost. Constraints are depicted in Fig. 1.
obvious because it is nof yet possible to produce Cost optimisation is difficult and -is subject to local
steel in large quantities, and economically, in a prices and conditions; for example, the same low
completely closed system with controlled oxygen sulphur levels in steel might be obtained by
chemical potential. 1MR/172
(i) hot metal treatment + converter (with sulphur
© 1988 The Institute of Metals and ASM INTER- lowered initially, and superheating) + ladle
NATIONAL. The author is at the Institute of Ferrous treatment either by top slag (large amount) +
Metallurgy, Technical University of Aachen, Aachen, rigorous stirring or by injection (small
Federal Republic of Germany.
quantities)
(ii) converter (with high sulphur initially, no
superheating) + ladle treatment as above, but
with larger quantities + longer treatment time
+ reheating.
INTRODUCTION Desulphurisation agents differ in price, in efficiency,
DEFINITION, MOTIVES, METHODS and in severity of refractory attack. For example,
Secondary steelmaking processes all aim to reduce costly CaO-CaF 2 flux powders react fast, show
where possible the time liquid steel remains in the greater refractory attack, and are needed only in
steelmaking (e.g. the basic oxygen furnace, BOF) or small quantities; cheap CaO-Si02-AI203 powders
melting (e.g. the electric arc furnace, EAF) furnace, react slowly, show smaller refractory attack, but are
and to confine the final making of steel between needed in larger quantities. The question is, which
tapping and teeming in a suitably equipped vessel. route, and with what desulphurising agent, repre-
Such processes are also known by the terms ladle sents the cheapest method under local conditions?
metall urgy, secondary refining processes, secondary
processes, secondary metallurgy, and post-furnace
treatment. The advent, growth, and intensive use of OBJECTIVES, MEANS, EXAMPLES,
secondary steelmaking has been one of the most MECHANISMS OF SECONDARY
significant developments in steelmaking during the STEELMAKING
past few decades.
The ultimate objective of ladle metallurgy is
A BOF is sufficiently well suited for decarburisa-
steelmaking under completely controlled conditions
tion, dephosphorisation, and nitrogen control, if
embracing the steel melt and its associated phases.
demands are not too stringent. It is only of limited
Detailed objectives are as follows:
use with respect to strong decarburisation and
nitrogen removal: there is no net hydrogen removal (i) homogenisation of the steel bath with respect
and steel cleanness has to be improved. Ladle to temperature and chemical composition
metallurgy can be adapted to overcome the above (ii) alloying, with minimum oxidation of the
limitations. alloying material, to give improved alloy
Modern steelmaking is a two stage process. The yield; compositional control within narrow
first stage uses primary steelmaking in BO F or EAF limits
for the production of a raw steel, which is then (iii) desulphurisation, deoxidation, inclusion
further refined in the second stage by various shape control, improved steel cleanness;
processes. The coupling of the two stages allows full dephosphorisation, high isotropy of mech-
utilisation of the capacity of the primary furnaces anical properties
and the production of high quality steel of all grades. (iv) decarburisation
It allows a clear distinction between oxidising (v) hydrogen removal, nitrogen control

International Materials Reviews 1988 Vol. 33 No.2 53

54 Lange Secondary steelmaking processes

feeding-in
equipment refining lance heating
(a)
~ e-
Iwire Injection I 102)

*
electrodes
~
(b)
Ii:
bottom injection lance injection
adding .\Powderl wire
gfrom top gas ~_.feeding

reactive
vacuum.
gas phase
IAr. N2, 021
(c) tV gas tiM -,,',t.
.~oj"o
-'.!IiI:
~
~~~-
'--- gas

~ ti t
slag
~,
permanent
phose contact
0

0
inert gas
stirring
Cd) \::::.:
~
~.~
ladle deoassino RH DH VOO
r
refractory

it rIf
0
lining
0

0
induction
coil
(e)
~
-·a _. A

[stirring) ladle furnace VAD ASEA-SKF

0
a separation of steel and slag; b stirring and homo-
.• genisation; c adding materials for reaction and alloying;
transitory d vacuum treatment; e heating
phase contact 2 Operations and reactors of secondary steel-
making (Ref. 2)
slide gate nozzle
t
. t gas s t·Irrlng
mer l
Ar, N2 and alloying without pollution of steel and
environment
1 Possibilities for after-treatment of steel:
model reactor (Ref. 1) (ix) methods to minimise lining wear.
Some examples of such methods are shown in Fig. 2
and given in the following list:
(vi) attainment of prescribed teeming tempera- (i) systems to cut off slag flow, such as slag ball,
tures within narrow limits slag stopper, tapping syphon, lime spraying
(vii) providing sufficient holding time during on to slag, slag skimming, suction of top slag
treatment and teeming out of the ladle
(viii) acting as a buffer between furnace and (ii) injection of gas with immersed lance,
casting unit. bottom, or wall injection devices (ladle
As yet, there is no single process which can perform
all these functions, the emphasis varying from
Table 1 Form of impurities and their influence
process to process. Their combination will vary
on mechanical properties (Ref. 3)
according to local requirements and will be carried
out in such a way as to guarantee only what is really Impurities Form Mechanical properties affected
needed to justify the treatment and the costs
involved. S, 0 Inclusion (i) Ductility
(sulphide and Charpy impact value, anisotropy
Means to attain the above objectives include the oxide) Formability (elongation,
following (Fig. 2): reduction of area and
bendability)
(i) methods to separate steel and slag after or Cold forgeability, drawability
during tapping (ii) Low temperature toughness
(iii) Fatigue strength
(ii) methods to stir and mix the materials within
C, N Solid solution Solid solubility (enhanced),
the ladle hardenability
(iii) methods to add materials for reactions and Settled Strain aging (enhanced), ductility
dislocation and toughness (lowered)
alloying Pearlite and Dispersion (enhanced), ductility
(iv) methods to decrease ~, Q, H, and ~ content cementite (lowered)
of steel Carbide and (i) Precipitation, grain refining
nitride (enhanced), toughness
(v) methods to avoid reoxidation, rephosphor- (enhanced)
isation, resulphurisation (ii) Embrittlement by intergranular
(vi) methods to meet required teeming tem- precipitation
P Solid solution (i) Solid solubility (enhanced),
peratures
hardenability (enhanced)
(vii) selection of suitable ladle and nozzle (ii) Temper brittleness
refractories (iii) Separation, secondary work
embrittlement
(viii) selection of materials suitable for reactions

International Materials Reviews 1988 Vol. 33 NO.2

 Lange Secondary steelmaking processes 55

Table 2 Summary chart for assessment of secondary metallurgical processes for achieving
metallurgical targets (Ref. 4, courtesy Steel Times)

Converter-based Ladle-based

atm
pressure Vacuum atm pressure

(VAD)
Objective Application module Approach* AOD ASM VODC VD VOD VD/LF RH AP IP LF

Decarburisation Oxidising Oxygen

top blowing • • • • 0
Oxygen injection
• • 0
CO purge-out CO pressure
reduction
()
• • • • •
()

Degassing Affecting the

gaseous phase
Admission of
Vacuum

Under vacuum
• • • • •
external gas pressure
Under atm
()
• • • • •
() ()
presssure
Deoxidation Via CO reaction Pressure reduction
(vacuum) • • • • •
• • •• •
Alloying Injection, etc. ()
Addition
• • • • • •
Desu Iph urisation Bath slag
reaction
Ar purging
with 1st slag
()
• •() () () ()

Ar purging
with 2nd slag • • • • • ()

Alloying Injection of
solids •
Adjustment of Alloying Addition
• • • • • • • • • •
analysis Reduction With CO reaction
(vacuum) • • • •
With alloying
agents • • • • • • •
Temperature
increase
Heating Chemical
Electric • • • • • ()
()
•
Improvement Purge-out Admission of
of purity external gas
under reducing
slag
• • • • • • () () () ()

* • High potential; () limited potentials; 0 requiring additional modules.

stIffIng, DH, RH), induction field (ASEA- (iii) dephosphorisation: slag high in CaO and
SKF), mechanical devices iron oxides, flux: CaF 2'
(iii) injection with carrier gas, oxygen blowing A1203, or Si02
(VOD, VODK, AOD, RH), wire feeding desulphurisation: slag high in CaO, low
(iv) use of vacuum (RH, DH) in oxides, flux: CaF 2'
(v) suitable lining, top slag, controlled atmo- A1203, or Ca, or Mg
sphere, such as vacuum, covered ladle metals
(vi) use of cooling scrap, arc heating (ladle deoxidation with Mn, Si, AI, Ca, Mg
furnace, ASEA or Finkl process), ladle cover dissolution, heat transfer, inert gas shielding
(vii) basic lining of low oxygen and sulphur (iv) dependence of reaction on partial pressure
potential (v) heat transfer
(viii) control of impurity level. (vi) resistance to mechanical, chemical, thermal
The following methods are used to exploit the attack
physical properties of and chemical reaction between (vii) purity, collecting emissions, recycling, con-
metal and slag: trolled deposition
(viii) dissolution by chemical and thermal
(i) different emissivity, electrical conductivity, gradients, proper control of metal and slag
specific gravity of steel and slag movements.
(ii) buoyancy, increasing phase boundary area,
shortening the characteristic length which
determines diffusion and heat conduction
time, increasing the probability of coales- BENEFITS AND POTENTIALITIES OF
cence and flotatioN of inclusion particles, LADLE METALLURGY
decreasing rate limiting thicknesses of phase A number of benefits are associated with ladle
boundary layers, dissolution of reaction metall urgy. These are reduction in furnace time,
products by top slag increase in overall production capacity, higher yield,

International Materials Reviews 1988 Vol. 33 No.2

56 Lange Secondary steelmaking processes

Table 3 Concept of clean steel manufacturing different combinations on the level of steel
and necessary functions (Ref. 3) impurities. Note that in this review hot metal
treatment is not explicitly covered. A recent review
Concept of clean steel
Element manufacture Necessary function
on this subject is available. 6
In addition to the metallurgical results given in
P Dephosphorisation at low Desiliconisation and Table 4, Table 5 gives collected data on the removal
temperature dephosphorisation of
molten iron
capacities of different units and on their suitability
Prevention of rephos- Removal of BOF slag with respect to alloying, temperature, and inclusion
phorisation by BO F slag shape control.
Dephosphorisation of
molten steel The levels of steel impurities obtainable are shown
S Desulphurisation of molten Desulphurisation of molten
in Fig. 4. It is claimed9, 10 that a total inclusion level
iron is not enough iron of
Comprehensive treatment Full deoxidation of slag and
must be applied to both molten steel (C+O+H+N+S+P) < 70 ppm
molten iron and steel Control of slag composition
Strong agitation of slag and can be achieved with the following specifications 11
molten steel
Securing of reducing
for each element:
atmosphere
C ~ 20, 0 ~ 10, H ~ 0·7, N ~ 15,
Total Prevention of reoxidation by Securing of reducing
oxygen slag and refractories atmosphere S ~ 5, P ~ 15 ppm
Accelerated floating of fine Acceleration of inclusion
inclusions floating by amalgamation
Long moderate agitation DEVELOPMENT OF LADLE
Tempera- Temperature drop Temperature elevation by
ture compensation during clean energy
METALLURGY
steel treatment The problem of hydrogen with big steel forgings
led to the vacuum treatment of steel in the ladle.
Hydrogen, nitrogen, and oxygen (as CO) could be
better quality, and improved reproducibility and removed, and, in addition, alloying and refining were
consistency in steelmaking. possible. The vacuum· degassing of killed steel did
Table 1 lists the influence of the usual steel not work efficiently because of the rapid decay of the
impurities on mechanical properties, demonstrating vacuum within the melt due to the rising ferro static
clearly why they should be properly controlled. pressure. Therefore stirring of the melt became
Table 2 summarises the various ladle treatments necessary. It was found that this was beneficial for
(columns) with respect to the objectives of ladle non-metallic inclusion removal.
metallurgy (rows). Continuous casting machines need control of steel
With respect to the control of P, S, total oxygen temperatures within very close limits, which can be
content, and temperature of steel, Table 3 indicates achieved with gas stirring alone. Continuous casting
what has to be done. Some examples for possible also means long residence time of steel in the ladle,
combinations of various processing units are given in which can be achieved by the replacement of the
Fig. 3 and Table 4. Figure 3 explains to some extent stopper rod by the sliding gate nozzle. This measure
the factors that determine the choice of a particular led to the use of hot ladles, which were then lined
method. Table 4 indicates in addition the effect of with basic ceramic materials, drastically decreasing

Table 4 Outline of NSR system (Ref. 3)

Equip- Molten iron pretreatment NSR

ment BOF
TDS KR VSC II' Lf: RH

c::
,Q
Cti
CaC2+ N2 O2

1
O2 Flux+Ar
Flux
cgno y

m lSL1
~ 1

& 17 m 6
~ J Flux
Vacuum

_dr-
bD
~ Vacuum
<=c::
0
u
If)
If)
(].)
u
0
'.
0:

Desulphuri- Desiliconi- Decarburi- Slag removal Desulphuri- Desulphuri- Dehydro-

(].)
zalion zation zation zalion zation genation
:§ Aimed-for quality
Dephosphori- Dephosphori- Deoxidi- Composit ion
::i zation level (ppm)
0 zation zation adjustment
Temperature
elevation [P] IS] [H] [0]

I 0 0 0 0 (0) 0 0 50 IO 1.5 15
E
~ II - 0 0 (0) 0 120 10 1.5 15
Cti 0 0
0.

C
(].)
III 0 - 0 0 0 - 0 120 20 1.5
E
Cti
(].)
IV 0 - 0 0 - - 0 120 50 1.5
r= V 0 - 0 (0) - - 0 120 50 1.5

International Materials Reviews 1988 Vol. 33 NO.2

 Lange Secondary steelmaking processes 57

3 Systems for refining steels extra-low in impurity element concentrations (Ref. 5)

the mean oxygen potential of the steel in the ladle.
The availability of basic ladles, gas injection, and
solid/gas injection from LDAC or Q-BOP steel-
making allowed the injection of calcium bearing
materials into the ladle with the resulting drastic
reduction of Q or S down to 10 ppm and inclusion
shape control.
Extended residence times and the melting
additions consume energy. This led to improvements
in the insulation of the ladles. A ladle cover and/or
an external heating system were provided. This
allowed decreased tapping temperatures (with bene-
fits with respect to converter lining, dephosphoriza-
tion, and the availability of an external heat source).
The desire to exploit fully the transformer capacity
of the electric arc furnaces and the poor desul-
phurisation capacity of oxygen steelmaking led to the
transfer of many metallurgical reactions (desul-
phurisation and deoxidation with Ca, degassing,
alloying) to the ladle, with the result that tap-to-tap
times of the electric arc and oxygen furnace
decreased, with a corresponding increase in smelting
and refining capacity.
Figure 5 shows the historical development of
equipment used in secondary steelmaking. Some
examples of the mysterious abbreviations appearing
in connection with ladle metallurgy are explained in
Table 6. The decline of ladle stirring alone and the
rising predominance of more sophisticated ladle
processes such as vacuum treatment or powder
injection can clearly be seen in Fig. 6:
OPERATIONS OF SECONDARY
STEELMAKING
SLAG SEPARATION
The control of slag composition is a basic
prerequisite of secondary steelmaking. The separa-
tion of slag from liquid steel is a very important
of practical problem if better metallurgical results and a
high reproducibility are to be expected. However, at
the very start of ladle metallurgy, i.e. during tapping,
it is very difficult to prevent some refining slag
entering the ladle, not only because there is some
pre- and after-flow of slag but also because vortex
formation during tapping drains some slag into the
receiving vessel.14, 15
Carryover of refining slag with a high oxygen
potential leads, for example, to rephosphorisation,
decreased yield of deoxidation and alloying elements,
and deterioration of secondary steelmaking reactions
under reducing conditions. Neutralisation of the
oxidising potential by reduction of (FeO) and (MnO)
with aluminium does not solve the rephosphorisation
problem. Moreover, when both an oxidising slag is
needed for steel dephosphorisation and a reducing
one for steel desulphurisation, slag removal becomes
essential.
The slag on top of the steel tapped from a BOF
usually arises from the following sources:
(i) slag carried over from BO F
(ii) reaction products resulting from deoxidation
and/or reoxidation

Table 5 Capabilities of ladle metallurgy (Ref. 7)

.1H2, .1N2, Inclusion Tramp

.1S,% ppm (%) ppm (%) .1°2' % Alloying .1 temp, K shaping elements

Porous plug,
synthetic slag -50/-60 +2/+3 0/ +20 -50 limited control No No
Lance injection -50/-80 +2/+5 +20/+40 -50 High recovery -40/-60 Yes No
Wire feeding 0/+2 0/+20 Varies Excellent -10/-15 Yes No
Arc heating -50 -50 Reproducibility + or- No No
Vacuum degassing
RH type (-80) (-30) -50 Excellent -50+ No Partial
DH type (-50) +20 -50 Good -50+ No No
Stream (-60) -50 No No No
Tank (-60) -50 limited -50 No No
VAD/VOD -70 (-80) (-50) -50 Excellent + or- No Partial
w/arc
CLU/AOD -70/-80 (-60) (-70) Good + or- Some No
(Bi, Pb, Zn)

International Materials Reviews 1988 Vol. 33 No.2

58 Lange Secondary steelmaking processes

N(ppm)

S(ppm) flux injection

in a ladle
deoxidation with
flux injection in a P(10ppm)
ladle
dephosphorisation
tapping without __
during tapping
deslagging and LF
deoxidiser
C(10ppm)
flux addition ---- decarburisation
in RH degasser in RH degasser
normal operation 50 30 15 8 6 4 2 1·5
with gas bubbling COMPOSITION
in a ladle

4 Achievable content of chemical composition using different secondary refining processes (Ref. 8)

Years Vacuum 1 Injection 1 Heating

1950 Gazal Pro~ess (Argon)

BV (also in USSR)
1952

Ar

j VAC'& ~.
1956 i OH (Hosch AG) 'f!'
1958 Finkl Process

1D-'~
VAC¥t
1959

;:~nstahl) Mil VAC :A j a

~er~
d·
1961
(Buchemerl .J...~ A<

j VAC\3i I (10 :E
rlJi
1964
1965

1967
VOOi
j..
v;:z'P A!...
"
AOO
~ ~
~M+O,
VAO.f{
j
(Finkl & Sons) _ ..
1!J
VAC
1968

g
RH-OB (NSC) -. - (Unl0'2-Carbide)

-1
Ar
1969
1970 AC ~ew development W~ ';....1;' Wire -

I L
rt
...-OJ In Japan NKK \: If - - __
1971 A, , (I I. \; LF (Nittoku)
1972
ni. A ASS (sum~ito~?)
' Slag

1973
H,·O+O,
=it ~
I
CLU
(Sweden) I
~
AlbUI~.:.~
:-:,
•..••;
~~~

Slag
Ar

1974

1975

Slag -
~,v .
CJ -
SCAT
(Sumitomo)
CAS (NSC)
SAB(NSC)
T'N (Germany)
Slag

f:
-

51/ .Cap" jtorage '-

a··

Ar
t:·
~l

tank
t,
Ar gas

. \,;;-Ar J . :
Ar gas : :

ii
mgot i . CAB(NSC) ..
1977 Rapid AI Feeder
J (Kawasaki)

1978
5 Development of various ladle refining equipment (Ref. 12)

International Materials Reviews 1988 Vol. 33 NO.2

 Lange Secondary steelmaking processes 59

100 Table 6 Various abbreviations

,7.7."1~r
ABS AI bullet shooting process (Sumimoto)
Powder
injection
BV Bochumer Verein
CAB Capped argon bubbling (Nippon Steel)
95 CAS/SAB Composition adjustment by sealed argon bubbling
Vacuum ·'-:~/ •••._
~
0 treatment
(Nippon Steel)
/ DH Dortmund-Harder Huttenunion
IP Injection process
0 Ladle Ar or N2 IF ladle furnace process
I- 90 stirnng NSR New secondary refining
«
a:: RAF Rapid AI feeder process (Kawasaki Steel)
RH Rheinstahl and Heraus
I- SCAT System of calcium adding technique (Sumimoto)
2 TDS Torpedo desulphurisation
lJJ TN Thyssen- Niederrhein
:I 85
VAD Vacuum arc degassing
I-
« VOD
VSC
Vacuum oxygen degassing
Vacuum suction cleaner
lJJ
a:: WF Wirefeeder process (Nippon Kokan)
I-
80
considered with caution. The height of the slag
remaining depends on its fluidity and the duration of
1975 '76 '77 '78 '79 '80
YEAR the treatment.
Currently, bottom pouring the steel into another
6 Change of treatment ratio of secondary ladle and leaving some steel to be recycled in the first
refining methods in BOF-continuous casting ladle ensures the highest degree of separation.19
process in Western World (Ref. 13)
Slag separation by reladling and/or slag skimming
is expensive and requires extra heat and ladles, but
(iii) dissolving of the ladle lining merits attention if it can provide an answer to the
(iv) partial remelting of the ladle slag, adhering to serious problem of slag separation.
the ladle wall from previous heats.
GAS INJECTION AND GAS AGITATION
This slag usually has a high oxygen potential, and
contains, in addition to iron oxides and (MnO), Stirring pattern
mainly lime, alumina, and silica (Fig. 7). General features of gas injection are detailed in
The slag-cut ball or floating plug has a predeter- Ref. 20, and, although not repeated here, are
mined. weight, which enables it to float at the important.
interface between the metal and slag. If properly The dependence of the volume of gas bubbles
placed above the tapping hole, it should block the detaching from a nozzle on the liquid properties and
tapping hole and stop the stream of molten metal at on design and operational parameters has been
the end of the tapping operation. With a slag-cut pot, investigated using a digital simulation model. 21,22
the same procedure is carried out in a second ladle The bubble detachment volumes increase at higher
on top of the teeming ladle. With a teapot spout interfacial tensions and lower densities of the liquid,
fitted to the BOF, the tap hole is always below the and are independent of the viscosity of the liquid as
slag level preventing preflow of slag. long as this is below 100 mPa s. The detachment
Mechanical slag stoppers of various kinds plug the volume is independent of the Laplace constant at low
tap hole physically at the instant slag is detected values of this constant, a strong increase being
during tapping. The use of ladle sliding gates as o bserved only at higher values of the constant. In
tapping valves allows reduction of the flowrate at the this region, the trend of approximation to a limiting
end of tapping. The amount of slag carried over law is evident. The cross-sectional area of the nozzle
should be minimised. With pneumatic slag stoppers has a great effect on the detachment volume at low
the tapping stream is cut off by blowing gas into the gas flowrates, its effect decreasing with increase in
tap hole from outside the vessel. gas flowrate. At high gas flowrates, the influence of
The differences in emissivity and stream diameter the gas flowrate dominates and the detachment
between slag and steel are used 17 to detect slag flow- volume increases more than proportionally with the
out. The radiation power of molten steel mixed with gas' flowrate.
slag is about 1·2 times stronger than that of molten In cases where small detachment volumes are
steel, while the radiation power of slag alone is about required, interfacial tension and dynamic viscosity
1·6 times stronger than that of molten steel. should be small and density high, with nozzle
Intermediate deslagging can to some extent be diameter and gas flowrate low. In steel, smaller
accomplished with a vacuum suction slag remover bubbles are produced than in slag, the bubbles
which lifts off slag on top of the steel. A jet of water produced in non-deoxidised and non-desulphurised
cools and granulates the slag into small particles. steel being even smaller. During deoxidation and
Owing to the necessity of keeping the nozzle of the desulphurisation, the bubble dispersion worsens, and
suction head a finite distance from the steel, a a particular gas flowrate should be divided among
residual slag layer of up to 50 mm thickness remains several small nozzles.
on the steel surface, although a thickness of only At the flowrates used for stirring, the fluid
10 mm has been reported.18 This figure should be dynamics in the ladle are governed by a buoyancy

International Materials Reviews 1988 Vol. 33 No.2

 slag carried over total slag in ladle
o < 600 kg < 1300 kg
o 600 - 1100 kg 1300-1800 kg
• 1100 - 1600 kg 1800 - 2 300 kg
• > 1 600 kg > 2300 kg
40
2eaO·SiOI,

3 CaO· SiOl,
20

20 40
[A1203] ,mass - 0/0

7 Concentration ranges of major constituents of ladle metallurgy slags (Ref. 16)

plume rather than a jet model. 23,24 In the highly
turbulent bubble plume, the stirring and mixing
actions are intense. As can be seen in the Figs. 8 and
9, the stirring action is small near the bottom of the
ladle and weak in the centre of the circulatory
movement, which proceeds upwards in the bubble
plume, outwards to the vessel wall at the top surface,
downwards at the vessel wall and back towards the
gas injection ,device at the bottom of the vessel. An
asymmetrically placed bubble plume gives velocities
near the bottom which might be of an order of
magnitude greater than for a symmetrically placed
plume.27
The liquid flow in the ladle occurs via bulk motion
of the metal along the streamlines and eddy diffusion
across the streamlines. Figure 10 shows the decrease
of the average velocities of the surface flow layers as
measured by a drag probe in a 60 t ladle at different
gas flowrates. After termination of the gas injection,
it takes 40-50 s for the near surface of the steel bath
to come to rest. 2 8
Very roughly, a characteristic velocity Vc for gas
bubbling, given by
(1)
where Q is the gas flowrate, g the acceleration due to
gravity, and H and V are the height and volume of
the bath, respectively, can be used to estimate
convective velocities. 27
The bubble plume from a single orifice has a
tendency to meander at a frequency of 2-3 s
(Refs. 28, 29).
Intense stirring of the metal/slag interface can be
efficiently performed by gas injection at the bottom
of the melt and application of a vacuum at the top.
The vacuum increases the bubble volume, thereby
causing a great number of large bubbles to cross the
interface, leading to high turbulence there.
At velocities above O·3 m s- 1 at the slag/metal
interface slag droplets (inclusions) may be entrained
by the metal flowing along the interface and into the

(a) (e)

a central; b off-centre, r/ R = 0-5; c edge, r= R

8 Different positions of porous plug and resulting flow pattern (Ref. 25)

International Materials Reviews 1988 Vol. 33 No_ 2

 Lange Secondary steelmaking processes 61

Flow

pattern

Dead
lone

cf C Relative faster flow (~~ Weak flow ///;/ Dead zone

9 Flow patterns of liquid solution by nitrogen blowing through porous plug at 1·5 I min-1 (Ref. 26)

27 suppresses the radial outflow at the water surface and

melt. With the energy balance
kinetic energy = surface energy
+ energy due to buoyancy
for a slag particle with velocity v to penetrate
through the slag/metal interface, the relationship
v ~ [48g(Pm-PSlag)O/P;lag]1/4
isderived30 to calculate the critical metal velocity at
which a slag particle can be entrapped in the metal
phase. With Pm = 7000 kg m - 3, Pslag = 3000 kg m - 3,
and (J = 1 or 0·5 N m -1, one obtains v = 0·68 or
0·57 m s -1, which compares favourably with the
o· 3 m s - 1 given above.
Figure 9 indicates that two recirculating vortices
might be too simple a picture of the real situation of
liquid motion in the ladle. Sucker et aI.31 show that
it is possible to create two circulatory loops across
deflects the water vertically downwards, increasing
the rate of turbulence energy dissipation between
plume and adjacent liquid at the expense of energy
transfer from the plume to the main bulk of the
liquid in the ladle. Therefore, for the same energy
input, less of the available energy is used with the
(2)
immersed baffle than without it.
In vessels with a taper, another recirculation zone
near the vessel wall and the liquid surface develops;
the vortex eye moves towards the vessel bottom.
Most of the high velocity region· is confined to the
vortex associated with the bubble plume, the other
0·6

"",,
the height of a ladle. At half the liquid height, there is 0·5
a horizontal liquid flow directed towards the bubble len
plume. Bubble columns show similar behaviour, the E
aspect ratio determining the number of circulatory I
>- 0·4 \ I
loops.
Additional solid walls placed in the path of the
t:
u
0
\
,'455
I
I
liquid metal change the stirring pattern. One way to
-~ I
...J • •••••••0
0460 ~_

make additions in an atmosphere of reduced oxygen ~ 0·3 .75

I
potential and to avoid these additions coming into <
W
255:~
0180
e410 "' ,, ~I
excessive contact with the top slag is to immerse a
U :13.70 c220 ~I
"-~
()150 140
.35
~ 095 "35
~I
refractory lined cylinder into the liquid steel at the a:: 0·2 (),25
0120
spot where the rising bubble/liquid plume creates the ::>
tJ)
""

',",30
0110 ~1
breakthrough eye in the slag layer. This is done in I
a:: ~~I~ ....., .,;..,30
I
the composition adjustment process by sealed argon <{ Qa:>~~,
I
w 0·1 ..... I
bubbling (Fig. 5), abbreviated sometimes to CAS or z
to SAB. " I
I
The water model flow field shows32 that there are
two distinct recirculating loops, the dividing line 0 0·5 1·0
nearly coinciding with the partially immersed, central DIMENSIONLESS RADIUS (rl R)
cylinder acting as a baffle. Beneath this cylinder there 10 Decay of near-surface velocities along radius
is a downward flow, leading to an upward flow in the of 60 t ladle at various gas flowrates; figures
plume (as usual) and at the vessel wall. The cylinder show gas flowrates in NI min-1 (Ref. 23)

International Materials Reviews 1988 Vol. 33 NO.2

vortex being relatively quiescent. The downflow close
to the rising bubble plume entrains a significant
amount of gas from the plume near the free surface of
the liquid. In industrial applications, the high
momentum liquid flowing out of the breakthrough
eye hits the refractory lined cylinder, and enhanced
erosion has to be expected, producing inclusions
which are carried downward.
Recirculation rate in gas stirred ladles
The mass flux AI (in t s -1) of entrained steel passing
through the top section of the bubble plume is given
by the following semi-empirical equation23,24
M= 13-3(H +O.S{ln(1+ 1~S)r5 QO"381
where the depth H of injection is in metres and the
gas flowrate Q in Nm 3 s - 1. With water model
experiments, 29,33 the relationship
Ail = 10·65(H + 1·46)1'127
x [In (I + 1~6) T12? Q~"549
is obtained, where Ql is in m3 s -1 at the temperature
T and the pressure p of the nozzle exit.
With H = 2·5 m, Q = 600 NI min-1, and Ql = 600
x (1273/298) x (1·46/2·5) I min -1, one obtains
Nt = 7·5 t s -1 and Nt 1 = 6·6 t s -1. The recirculation
time of a 185 t melt is then about 25 s; for a 60 t melt,
it is about 50-20 s, when the gas flowrate increases
from 20 to 200 NI min - 1.
Mixing time
Mixing in the bulk liquid with a bubble driven flow is
achieved on the macro scale by buoyancy driven
forced convection from the bubbles rising in the
plume, resulting in macroscopic entrainment of
liquid in the plume; on the micro-macro scale mixing
is by entrainment of liquid in the wake of the
individual bubbles.
Mixing time or time to reach homogenisation is
defined as being the time which elapses between the
addition of a tracer to the bath and the moment
when its concentration reaches a preset fraction of
the final concentration. This can be approached only
asymptotically with respect to time. With visual
observations, mixing time can also be defined as the
time in which a certain criterion is reached (e.g. a
change in colour). Mixing time values obtained with
different methods ·are rarely directly comparable.
The mixing time should not be confused with the
time refining reactions need to come to equilibrium.
The mixing time is only an indication for the
conditions of stirring prevailing in a vessel. Of
course, good mixing conditions promote the rates of
refining reactions, but mixing time is not necessarily
equal to the time refining reactions need to reach
equilibrium.
Zlokarnik34 was one of the first to investigate the
homogenisation of liquids with centrally bottom
injected rising bubbles. He determined the relevant
Internationar Materials Reviews 1988 Vol. 33 NO.2
dimensionless numbers and found with water models
that, for the mixing time r
r/dbath = 4'75(hbatJ~as)0'5(dnozzIe/g)0'25 (5)
Decreasing interfacial tension and viscosity decreases
mixing times. At a kinematic viscosity above about
200 mm2 s -1 (with steel it is about 1 and with slag
10 mm 2 s- 1), practically no. homogenisation is
possible. This investigation has been followed up by
many other workers.
The mixing time decreases with immersion depth
of the lance, with increasing gas flowrate,22, 35-37
and movement of the place of injection to coincide
with trIadIe35 or at -trIadIe.38For the same gas
flowrate, the mixing time decreases if the centrally
(3)
placed injection nozzle is replaced by an eccentric
nozzle or if the gas is injected with two nozzles. 39,40
With a water model and two rows of three
symmetrically placed nozzles, Koria and Lange41
found the following results:
(i) scrap increases mixing time
(ii) increasing the scrap ratio increases mixing
time
(4)
(iii) homogenisation is possible within a definite
time only up to a certain maximum scrap
ratio
(iv) increasing the flowrate of the bottom gas
decreases mixing time
(v) increasing the aspect ratio of the melt
decreases mixing time
(vi) the mixing time r in seconds can be correlated
with the agitation power w in W m - 3 related
to the bath volume
r = [exp (4·338+0·006%~)J
x (Whb/dbYO'00847%~-0'5564) (6)
where ~ is volume of scrap (as a percentage)
of the bath volume. The influence of the
aspect ratio 'bath height/bath diameter' is
combined empirically with the power density
just for simplicity.
The mixing time increases if there is slag on top of
the steel bath and if the relation between vessel shape
and place of gas injection favours the existence of
extended stagnant regions, as can be found in a ladle
with a cylindrical baffle placed around the break-
through eye32 or in a torpedo car (Fig. 11). The way
in which lance design shortens the mixing times in
torpedo cars has also been investigated.43
Figure 12 shows the tracer dispersion within a 50 t
steel ladle stirred by bottom injected gas. The
homogenisation time decreases with gas glowrate,
approximately 4-5 NI t-1 (normal litres of gas per
tonne of steel) being needed for homogenisation in
this case. Another source45 reports that a stirring
time of 1·5 min with 750 I min -1 for a 190 t melt is
sufficient to achieve homogenisation. From this, one
can calculate the amount of gas required for
homogenisation as 6 I t -1 .
Figure 13 shows the tracer dispersion within a 40 t
steel ladle when no gas is injected and when only free
convection stirs the melt. Free convection provides
some agitation, but the final tracer· concentration
obtained with a 30 s bubble stirring with a deeply
 Lange Secondary steelmaking processes 63

GAS FLOWRATE) lmin-1 4 (a)

8 20 40 80 130 3
500 2
300 Torpedo K Fr-1 1
car -0
Ul 200' ! ! J- 0 1 2 3 4 5 6 7 8 9 10

~4 '-14·3 (b)
~ 100 ',/J Ladle
>- 3
i= 70 ... ~it/-..
.••..••.
'I Sf t:: 2 -
~ 50, With eJg >
z i= 1
°vt st'a' ..., , Uo
~ 30 «
o 0 4 5 6 7 8 9 10
o without slag
~ 20
• with slag ~4 (c)
0:::
3
2 4 6 10 20 40 60 100 ~2
lJ..
E )
W t-1 U 1
wo
11 Time required for complete mixing of bath as B; 0 2 3 4 5 6 7 8 9 10
function of input energy of stirring (Ref. 42)
4 (d)

3
immersed lance is lower than that produced by 2
natural convection. Clearly, the argon stirring has 1
reached stagnant regions which were previously o
unaffected. o 2 3 4 5 6 7 8 9 10
Several equations and approaches have been put TIME AFTER TRACER INPUT) min
forward by various groups to correlate the flowrates a 20 NI min-1; b 20 NI min-1; c 50 NI min-1; d 120 NI min-1
of the injected bottom gas with the resulting mixing 12 Typical examples of response curves in VOD
times. Although these equations are better than furnace (Ref. 44, courtesy Steel Times)
nothing and are of high practical value, some work
still needs to be done. These equations are
empirically developed and usually adapted to the height, and decreasing bath diameters. If there are
local circumstances. Correction factors are readily gas producing reactions within the steel bath (e.g.
introduced, but not explained. Mixing times are CO production or Hand N diffusion into the gas
usually not defined. The feedback of the metal- bubbles), then an increasing quantity of gas and
lurgical effects produced by the stirring gas (as greater gas agitation power are available, resulting in
increased CO production) on effective gas agitation decreasing mixing times. This explains why the
is not taken into account. points with mass transfer in Fig. 14 move to the right
In Turkan and Lange's computer-aided process and towards the lower edge in comparison wiTh
simulation (CAPS) calculations22, 47 of the processes those without mass transfer.
occurring within a steel bath on injection of gas the
velocities within the melt are determined as a
79
function of the bottom gas injected. The model of
Bhavaraju et al.48 and Sano and Mori49 has been
used to determine the energy dissipated by the
circulating melt owing to the motion induced by the 10
rising bubbles. In this model at steady state, the
energy input due to the rising bubbles is counter-
balanced by viscous energy loss in the turbulent
eddies. The results are shown in Fig. 14. The mixing 8
u
time is defined as the interval required to attain a
95% equalisation of the concentration difference of u
an added tracer. The liquid in the plume zone is well
mixed and usually has a higher velocity than the
liquid next to it. Therefore the mixing time in Turkan
and Lange's simulation model is assumed to be
governed by the circulation rate of the annular
downstream zone. .
The calculations demonstrate the influence of the o 2 4 6 8 10 12 14
gas flowrate, the vessel dimensions and the mass TIME~ min
transfer. The mixing time decreases with increasing 13 Tracer dispersion by free convection in 40 t
gas flowrate of the injected gas, with increasing bath heat (Ref. 46)

International Materials Reviews 1988 Vol. 33 No.2

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International Materials Reviews 1988 Vol. 33 NO.2


A further important observation is that bubbles
which do not traverse the whole bath height
contribute less to agitation. Bubbles of CO produced
in the upper parts of the melt agitate less than those
produced at the bottom. The influence of bubble
break up is also considered. Taking into account the
break up of the bubbles and mass transfer leads,
among other things, to shorter mixing times owing to
the higher induced mixing power.
The addition of solid particles to the gas injected
decreases mixing times. 50 In the literature, results are
available on calculated flow fields of bubble stirred
melts derived from turbulence models.
Temperature homogenisation in a steel
bath by gas injection
The steel melt in the ladle loses energy across the
ladle wall, the bottom, and the bath surface. The
colder parts of the melt, being denser than the hotter
ones, move to the bottom of the ladle, and
temperature stratifications develop.
The heat flux density j can be described 24 by
]. = a (Lmelt - fsurroundings )/t 1/2
where a ~ 1100 for sand lining and 1700 for
dolomitic lining in J S1/2m - 2 K -1.
Heat losses through the slag layer depend on the
thickness of this layer and its heat conductivity. Low
surface temperature of the slag layer drastically
decreases heat losses due to radiation. Usually these
heat losses are below 10% of the losses across the
lining.
Stirring with gas bubbles is a dependable and
cheap method for temperature homogenisation of
steel held in ladles, as long as the bubbling continues.
However, there is rapid re-establishment of tempera-
ture gradients once stirring has stopped: in a 7 t melt,
thermal gradients reappear approximately 2 min
after termination of argon stirring.28
Gas injection rates*
Grabner and H6ffgen have collected together
literature data on gas injection. 51 From this data,
one can derive the following specific gas injection
rates:
stirring < 5 NI min -1 t-1
lime steel desulphurisation 14 NI min -1 t - 1
VAD desulphurisation <2 NI min-1 t-1
In comparison with these data, the injection of
25- 50 NI min - 1 t - 1 of gas is strong stirring.
The removal of nitrogen with argon scavenging
from high alloyed steel has been achieved with52
50 NI min - 1 t - 1.
High gas flowrates need large freeboards. Lack of
large freeboard and splashing often limits the
maximum rate of gas injection.
* Unless otherwise specified, injection rate units refer to normal
litres of gas and tonnes of steel.
Lange Secondary steelmaking processes 65
GAS INJECTION AND MASS
TRANSFER
Gas-liquid transfer
Mass transfer between bubbles and the surrounding
liquids is described in a CAPS treatment22 of various
aspects of gas injection by the' expressions of the
penetration theory for the mass transfer coefficient p
p2 = 4DJnt,.t = 4Diu/nl (8)
where Di is the diffusion coefficient of substance i, u
the slip velocity of the bubble, and 1 the contact
length. The retarding influence of surface active
elements is taken into account by an additional mass
transfer resistance. The model calculates individual
values of slip velocity and contact length according
to local conditions for each bubble.22, 53,54
Some important results of Turkan and Lange's
CAPS treatment are as follows. Bubbles without
break up do not reach a stationary velocity: they rise
with an ever increasing velocity and are subjected to
a nearly constant acceleration, the value of which
depends upon the intensity of mass transfer. They are
seldom saturated with respect to the gas to be
purged, and there is a heavy feedback of the intensity
(7) of the mass transfer, via bubble size and circulation
velocity of the liquid, on the scavenging action of the
bubbles, on their stirring power, and on recirculation
rate. Neglecting this feedback gives erroneous
estimations of, for example, the stirring power
induced by the injected gas.
Liquid-liquid transfer
Kitamura et al.55
have established quantitative
relationships between the degree of deoxidation,
partition coefficient of sulphur, and rate of hydrogen
removal, and the work done by argon stirring, by
multiplying the stirring power per unit weight of
molten steel, according to the Sundberg equation,
with the time of vacuum treatment under 1 Torr in a
ladle.
A number of results are also available which relate
rate constants for slag-metal exchange reactions with
stirring gas flowrate, as, for example, for decarburisa-
tion in AOD,56 for the transfer of copper from top
slag to the melt,36 or with specific stirring power in
W t-1, as, for example, for oxide particle removal, 57
for transfer of nickel, 58 and for dephosphorisation of
hot metal3, 59,60 and steel. 3,59,60
The relationship
kp = 0·148°·68 (9)
with 8, the specific stirring power, in kW t-1 and k
in min - 1, has been given. 59 p
The rate constants usually increase with flowrate
or specific stirring power either linearly or, very
occasionally, asymptotically. As long as they increase
linearly, the end of the beneficial influence of stirring
on overall transfer acceleration has not been reached.
The mass transfer between two immiscible non-
dispersed liquids agitated by an inert gas pur~e has
been modelled with a mercury layer and an aqueous
layer, which are both agitated by bubbles injected
with a centrally placed lance near the vessel
International Materials Reviews 1988 Vol. 33 No.2
 66 Lange Secondary steelmaking processes

o In uctlon stlrrlng N .,. o Induction Stirr ing (N) __ ld

5000 A Induction
• Gas bubbling
stirring!(R~
y ~ 50000 A Induction stirr lng (R) J:J-r;g 0
• Gas bubbling ~~~
2000
• /. g____ ~O ~A A
20000 o Powder injection-cfu
.,.--- ".----
N
.....

b
oX
III
1000
500
//0
Up ...8 ~
/ ~

---------
0"" 6.____
.A
A ~
~
0
.Yo
E
10000
5000 -I~ .-.""" o~
o-~
UpCO----- A----;;-A
200 (mooel )metal
100
d~n-A------- (model)slag
2000
1000 Adown
~ --

10 20 SO 100 200 500 1000

1000 2000 5000 10000 20000 50000
EV -2/3, Wt-1 m-2 E V-2/3, Wt-1 m-2

16 Relation between mass transfer coefficient

15 Relation between mass transfer coefficient
in metal phase and power applied (Ref. 62)
in slag phase and power applied (Ref. 62)

bottom.61 As a model reaction process, quinone Solid-liquid transfer

dissolved in the aqueous phase is reduced at the
mercury phase, which acts as a cathode. The mass
transfer data are given by
Sh = 1· 33Reo'70 SC1/3
with the Sherwood number Sh = Pdbubble/ D and
the Reynolds number Re = USgVdbatlJVslaJ!' whe~e
sgv stands for the superficial gas vel~cIty, V. IS
the kinematic viscosity and Sc the SchmIdt
number. If this relationship is applied to the steel
layer in a steel bath (kinematic viscosity
7 x 10 -7 m2 s -1) of 3 m diameter, 3·5 m height, and
weighing about 175 t, and subjected to an injection
rate of 10 NI min -1 t - 1, the no slag droplet
formation should occur (as checked with equa-
tion (2)). One obtains ShSC-1/3 = 1240 or with
Sc = 150, D = 5 X 10-9 m2 S-1, dbubble = 50 mm,
P = DSC1/3d-1 x 1240 = 0·65 mm S-1. .
With a water model and a kerosIne solutIon
saturated with benzoic acid added to the water
surface to simulate the slag phase, the mass transfer
coefficient k in the slag phase is obtained from
measurements of the concentration change of benzoic
acid transferred to the water.62 The mass transfer
coefficient increases with the power (W t - 1 m - 2)
a pplied per tonne of liquid and the slag volume
raised to the power of 2/3 (Fig. 15).
Mass transfer across the metal/slag phase boun-
dary in gas stirred systems which do not show
interfacial turbulence can be described63 with the
individual mass transfer coefficient Pi in metal or slag
Pi = (bDiQ/F)1/2
of substance i, where Di is the diffusion coefficient, Q
the total gas flowrate crossing the phase boundary
area F per second, and b = 4 mm - 1 for the upper
phase control and 9·5 mm -1 for the lower phase
On dissolving- aluminium spheres in liquid alumi-
nium it is found65 that the coefficients for mass and
heat transfer increase with the flowrate of the gas
• (10) injected below the sphere. 2"
With room temperature models6 In WhIch
particles coated with KCI or benzoic acid were added
to the surface of water or injected with carrier gas,
the results shown in Fig. 16 have been obtained. The
mass transfer coefficient km in the model metal
increases with the power applied/tonne of liquid and
= the metal volume raised to the power of 2/3.
Comparing Figs. 15 and 16 shows that, for the
same stirring power, the ratios of mass transfer
coefficient to diffusion coefficient are much larger for
control in the metal phase (Fig. 16) than for control
in the slag phase (Fig. 15). In the case where the
diffusion coefficients of the benzoic acid do not differ
.
significantly in both phases, it must follow that the
stirring gas promotes reactions in the melt but hardly
influences the top slag. Reliance must then be placed
on other mechanisms for mass transfer enhancement,
as, for example, re-emulsification of the slag into the
bath or vice versa.
Figure 17 shows, for the dissolution of i~mersed
carbon rods in gas stirred melts, an area wIth very
high mass transfer in the bubble plume close to the
melt surface. Additions for reactions should be made
into this region for the most favourable effects. The
metal surface (b)
metal surface (a)
. (11)
G)
lI)
lI)
(1)

control. Riboud and co-workers19,64 give a much ni >

~
larger value for b of 250 mm - 1 (for the gas at the 4j 4j
temperature and pressure of the interface) and lI)
lI)
lI)
lI)

make no distinction with respect to phase control. 11I eLI

> >
With b = 250 mm-l, and D = 5 X 10-9 m2 S-1,
Q = (1·73 x 1900 x 1·48)/(298 x 3·5) m3 min -1 for a
steel bath at 1900 K of 3 m diameter and 3·5 m
height, a value of P of 3·7 mm S-1 is calcula~ed. ~his
value is very high and indicates slag emulsIficatIon. vessel bottom vessel bottom
With b = 10 mm -1, one obtains nearly the same 17 Schematic description of distribution of
value (P = 0·7 mm S-1) as in the example 1!sing mass transfer in a inductively stirred melt
equation (10), where there is no slag emulsIficatIon. and b gas-stirred melt (Ref. 58)

International Materials Reviews 1988 Vol. 33 NO.2

 Lange Secondary steelmaking processes 67

Table 7 Comparison of equations (12)-(16) Table 8 Comparison of equations (17), (18), and
(20)
Sh Se-1/3
Bubble stirring Rotation stirring (Se- 2) Se-1/3
Column Bubble stirred Aerated
Equation Equation Equation Equation Equation Rep Equation (17) Equation (18) Equation (20)
Re (12) (13) (14) (15) (16)
1 0·55 0·36 0·45
103 29·3 8·3 10·7 11·5 13·1 5 2-0 1-2 1·5
104 78-7 45,6 60-0 53-6 65,6 10 3·4 2·0 2·6
105 211·9 250-5 337-4 250-7 328·9 50 12'1 6-8 8·8

influence of CO bubbles produced on the dissolution beads, which ensures that the rate determining step is
of graphite rods immersed in oxygen containing steel external mass transfer. There is no effect of the
melts has been investigated.66 The resulting enhance- geometry of the column used,70 and the mode of
ment is described by the following equation introducing turbulence to the liquid does not affect
Sh = 1·5Reo-43Sel/3 . (12) the Sherwood number if the same power dissipation
occurs.
with Re = ud/v1, where u is the relative velocity Marrone and Kirwan 71 also quote an equation
between steel and graphite rod and d the rod from the literature
diameter. A similar relation holds for the dissolution
of sugar in bubble stirred water.
Sh = 2 + 0'45Re~-76 Se1/3 . (20)
In an investigation with gas stirred ladles, a for bubble columns and aerated vessels.72
comparable relation A comparison of equations (17), (18), and (20) (see
Sh = 0'05Reo'74Sel/3 . (13) Table 8) gives, for d~ = 0-1 mm, e = 100-1000 W t-1
(or at most 10 W t-1 in the BOF) and
where u is the maximum near surface velocity and d 7 2
v = 7 X 10- m S-I, roughly speaking the same
the rod diameter, is obtained for the dissolution of values, although equations (18) and (20) for
carbon rods at the plume/slag contacting edge.28 bubble stirring appear with slightly lower values
High mass transfer rates are found inside the bubble than those for the bubble column. With
plume, at the plume/slag contacting edge, near the Se=150, D=5x10-9m2s-1, dp=O'lmm, and
wall, and at the bottom of the ladle. (Sh - 2)Se - 1/3 = 1 or 10, one arrives at f3 = 0·4 or
A comparison of relationships (12) and (13) with 3 mm S-I.
some results for the dissolution of rotating, solid steel For small particles and modest power input, the
(equations (14) and (15)) or Cr203 rods (equa- coefficients for solid-liquid mass transfer are of the
tion (16)) into molten Fe-C or Fe-10Cr-C alloys is same order of magnitude as liquid-liquid transfer.
of interest67-69 With larger power inputs, they can be compared with
Sh = 0·06Reo-75Sel/3 slag emulsification.
· (14)
Sh = 0·112Reo·67 SeO'356 · (15)
Sh = 0·104Reo·7°Sel/3 · (16) STIRRING BY INDUCTION
The magnetic forces due to an induction field cause
Neglecting for the time being the small differences in
liquid metal to move. Depending on the direction of
the power of the Schmidt number, approximately the
the induction coil and the current passing through,
same values are obtained (see Table 7). With
different modes of fluid flow are possible:
Se = 150, D = 5 X 10-9 m2 s-1, drod = 30 mm, and
Sh Se-1/3 = 10 or 300, one obtains f3 = DSel/3dr~J(10 (i) circular rotational motion parallel to the ladle
or 300) = 0·01 or 0·3 mm S-I. This means that, even axis
for rather high velocities, the mass transfer coeffi- (ii) transverse motion across the ladle cross-
cients for solid-liquid transfer are smaller than those section
for liquid-liquid transfer. (iii) combination of vertical and transverse motion
The empirical equations to give a screw type helicoidal motion.
Sh = 2 +0'55Re~-79Sel/3 · (17) In principle, the liquid metal movement produced
Sh = 2+0'36Reo-75Sel/3 can be any combination of motion in the vertical or
p · (18)
horizontal planes, as in stirring during continuous
for bubble columns 70 and sparger stirred liquid,71 casting; however, as yet there has been no
respectively, with application to ladle metallurgy, with the exception of
(i). The direction of motion is easily changed by
Rep = d:/3S1/3/V1 · (19)
alternating the direction of the coil current.
as a modified Reynolds number, where dp is the Induction stirring through the steel shell of a vessel
particle diameter in metres, s the power dissipated presents a special problem. Iron considerably reduces
per unit mass of liquid in m2 s - 3, which is the the density of the magnetic flux reaching the steel
average power input to the fluid per unit mass in melt. To allow the magnetic field produced by the
W kg - 1, and VI the kinematic viscosity of liquid in stirrer coil to penetrate into the melt the ladle wall
m2 s -1, are obtained with room temperature model should be made of non-magnetic material and/or a
experiments with ion-exchange reactions using resin low frequency magnetic field should be used. Up to

International Materials Reviews 1988 Vol. 33 NO.2

68 Lange Secondary steelmaking processes

the pr~sent, austenitic steel is used as a non-magnetic 8

• PM strong mixing
matenal, but non-metallic composite material is also
oPM weak mixing
offered as a casing. Each of these measures however A Ar bubblmg
involves extra cost. " 6
Normal induction stirring does not strongly affect
the steel surface. Figure 17 shows that, for the
di.ssolution of immersed carbon rods in inductively I
-
0
t\I
0

S2 4
stIrred melts, there are areas of high mass transfer ..••...•.....•...•.. _- _----...A.
r:r ,Jr ~---- Ar
close to the vessel wall. Near the slag/metal interface, ~ 'lCJI.
the mass transfer is low except for the region where
the flow changes to vertical downward direction. It is 2 "
into these regions that alloying additions are most
favourably made.
There are further fundamental differences between 0
gas or induction stirring. Gas stirring needs as a o 2 4 6 8 10
prerequisite the introduction of another phase, the TIME, min
gas, into the melt, whereas with induction stirring a 18 Change in Cu and pulsation mixing (PM)
two phase system is not necessarily produced. Slag treatment after addition (Ref. 75)
can be stirred directly by gas, but not by induction.
A direct comparison58 between different stirring
m.et~ods shows that, at the same power input, gas bath a stirring energy sufficient to attain a better
stIfnng produces higher transfer rates and a stronger agitation in the bulk of the metal, while the layer
positive dependence on stirring power than induction near the slag/metal interface is kept as quiescent as
stirring. Similar observations have been made earlier possible. The stirring energy density is estimated as
where it was found that induction appeared to be les~ 10 W t-1 and is of the same order of magnitude as
efficient than gas stirring in reducing the hydrogen RH units. Perfect mixing times as measured by
content of an already fully killed steel in the ladle.73 copper tracer dispersion are 1·5-3 min (Fig. 18).
This observation can be readily explained by the The process utilises the kinetic energy of the
absence of scavenging action of CO in the fully killed molten steel flowing into or out of the tube. The
steel. The CAPS results of Turkan and Lange54 stirring action at the ladle bottom is claimed to be
clearly show the enhancement of the scavenging quite strong, but is comparatively weak near the bath
action of any stirring gas by other gases which diffuse surface, thereby decreasing the probability of Al
into a bubble, this enhancement being strongly contaminating the steel melt by top slag. Con-
dependent on the intensity of mass transfer into the sequently, loss· of Al and pick-up of P are less than
bubbles. with argon stirring.
The results62 presented in Figs. 15 and 16 also The principle of pulsation mixing is as follows. A
indicate the lower efficiency of induction stirring on refractory tube (MgO-Cr203 in the lower part) is
mass transfer, as compared with gas stirring. immersed by a swivel lifting mechanism into the
liquid steel in the ladle. The molten metal in the tube
is subjected to up-and-down motions by the sequence
MECHANICAL STIRRING of pressure changes due to charge and discharge of
Stirring by mechanical devices can be done by inert gas into and out of the tube. The process is
rotating, spinning, shaking, and tilting vessels, or by operated within a pressure range of 0·2-1·5 bar.
paddles and propellers. None of these possibilities Precise pressure control is essential to obtain
has so fat been used in secondary steelmaking. Only optimum stirring intensity and to suppress metal
in the treatment of hot metal are paddles and splashing in the tube which leads ultimately to
propellers used, because of the lower temperature of clogging.
the hot metal in comparison to steel. The only
mechanical stirring which is applied stems from
pouring steel, either from one vessel to another, from Table 9 Stirring powers for different patterns
and regimes
recirculating steel in RH, or from moving it up and
down as in DR or PM (pulsation mixing) processes.
Stirring pattern Power, Wm-3
One limitation of mechanical stirring on tapping
consists in the limited time available to take Gas stirring
5 I t-' min-'; 1 bar 1500
advantage of the tapping energy. It might be shorter 5 I t-' min-'; 0·1 bar 3200
than the time needed for reaction, e.g. dissolution of 1 I t-' min-'; 1 bar 300
added deoxidising or alloying elements. In this 1 I t-' min-'; 0·1 bar 600

respect, the perpetual stirring action in RH, DH, and Tapping steel
height, 1 m; time, 10 min 115
PM vessels overcomes this limitation. The stirring height, 1 m; time, 3 min 400
patterns of the RH and DH vessels are described height, 5 m; time, 10 min 600
under the vessel heading below. height, 5 m; time, 3 min 2000

The purpose of the PM process 74-76 is to create RH 600-800

DH 500-700
another flow pattern, as with gas stirred ladles, where ASEA-SKF 50-200
the surface of the bath is strongly agitated, but the PM (Ref. 76) 10 W t-'
DH (Ref. 77) 10Wt-'
bottom of the bath only weakly so. It should give the

International Materials Reviews 1988 Vol. 33 No.2

 Lange Secondary steelmaking processes 69

Table 10 Materials' for reactions and alloying by boundary activates interfacial mass transfer, leading
injection with carrier gas (Ref. 24) to the reduction of slag by deoxidising elements,
phosphorus reversion, and oxygen and nitrogen pick-
Dephosphorisation CaO + CaF2 + Fe203 + mill scale up from the atmosphere.
Soda
In Table 9, specific stirring powers are compared.
Desulphurisation CaO + (CaC03)
CaO+AI
Apart from the indicated exceptions, the data were
CaO + CaF2 + (AI) obtained from Ref. 78.
BF slag
Soda
CaC2
CaC2 + CaC03, CaO INJECTION OF SOLID PARTICLES
Mg+ (MgO, A1203, chlorides, slag)
Mischmetall
WITH CARRIER GAS
Deoxidation AI Principles and mechanisms
CaSi }
CaSiBa inclusion shape control The main purpose of particle injection is the feeding
CaSiMnAI of a fine grained material deep into the molten steel.
Alloying FeSi The major factors influencing this injection are as
CaCN2
Graphite, coke fines
follows:
NiO, Mo02
FeB, FeTi, FeZr, FeW, SiZr
(i) nature of the powder
Pb, FeSe, Te (ii) powder size distribution
(iii) gas and powder/gas ratio
(iv) injection depth.
CHOICE OF STIRRING PATTERN The nature of the powders used is governed primarily
Correct stirring is of the utmost importance. It by the purpose of the injection. A summary of the
should be known when to stir what, and how powders used is given in Tables 10 and 11, together
vigorously, for· the adequate promotion of transfer with a comparison between CaO- and Na2C03-
rates, and when just to move the melt slowly for based powders.
homogenisation. The optimum powder size has to be determined as
There are metallurgical reactions which require a compromise between fine powders (creating
strong mixing of metal and slag (e.g. desul- theoretically a large reaction surface, but possibly
phurisation and dephosphorisation), whereas others choking the nozzle, remaining entrapped within the
require gentle mixing at the metal/slag inter- bubbles, or being carried away by the dust collecting
face and maintenance of an unbroken slag layer system) and coarse powders (creating small reaction
(e.g. deoxidation and inclusion removal). Vigorous surface, but having a greater chance to leave the
mixing of metal and slag is achieved with gas stirring, gaseous envelope and to react with the steel bath, but
less disturbances at the metal/slag interface can be with shorter reaction time due to greater buoyancy).
obtained with RR, DR, PM, and induction stirring. Nominal particle sizes less than 2 mm, usually 0'1-
The demand for gentle stirring is intensified by O· 5 mm, are recommended. Specific surfaces of up to
improper control of slag carryover: any turbulent 0·2 m2 g-l powder are obtained. The powders can be
flow in the neighbourhood of the slag/metal phase mechanically mixed, or premelted and granulated.

Table 11 Principal iron and steel refining fluxes and comparison

between CaO- and Na2C03-based fluxes (Ref. 3)

Use Flux

Molten iron Desiliconisation CaO-Fe oxide

Desu Iph urisation CaC2-(CaC03), CaO-(AI), CaC03, Na2C03, Mg
Dephosphorisation CaO-(CaCI2, CaF2)-Fe oxid~, Na2C03
Molten steel Desulphurisation CaO-CaF2, CaO-Si02-AI203-(CaF2), Ca-CaF2
Dephosphorisation CaO-(CaCI2, CaF2)-Fe oxide, Na20-Si02, Ca-CaF2
Cleaning CaO, CaO-AI203, CaO-Si02-AI203, CaO-CaF2

Comparison between CaO- and Na2C03-based fluxes

Simultaneous
Thermal dephosphor- Waste
wear of isation and gas/slag
Cost refractories desulphurisation Siagging disposal

o o x x o
CaO-based 1 1 80 and 50% Impossible No problem
desulphurisation without CaF2
by addition of and CaCI2
CaCI2 and O2
x o o o x
Abo'ut four About ten Possible Melting point: Solution
times times 852°C required
boiling point:
Q
1387 C

International Materials Reviews 1988 Vol. 33 NO.2

70 Lange Secondary steelmaking processes
The coupling force between carrier gas and
particles which causes them to be accelerated is given
by79
. (21)
where f}p is the volume fraction of particle and CD the
drag coefficient of particle. High density nitrogen is
more effective than low density helium in acce-
lerating the particles. The flow is coupled when the
particles are so densely packed that their velocity
boundary layers overlap each other.
When the gas carrying the solid particles enters the
liquid, the particles proceed in almost a straight line
at constant velocity within the cone angle of the
particle jet, while the gas rapidly loses its velocity.80
The jet velocity decay is at first governed by the
liquid entrainment: inertia causes the velocity to
decrease rapidly. A low momentum jet is quickly
dissipated by the buoyancy force and spreads readily,
and lightly laden jets penetrate less deeply than
heavily laden jets. The gas jet breaks up into a cloud
of bubbles that rise through the liquid owing to
buoyancy, and, as this happens, particles trapped in
the bubble hit the gas/liquid interface, where they
will either pass through the interface or remain
trapped inside the bubble owing to frictional or
surface tension forces. Once the particle has entered
the liquid, its subsequent movement depends mainly
on the buoyancy and drag forces acting upon it.
For uncoupled flow, the gas and particles separate
at the lance tip on contact with the liquid, the gas
rising as bubbles; for coupled flow, gas and particles
move together for some distance into the liquid. As
the jet velocity decays, the coupling force decreases,
and the gas then separates from the particles, spreads
away from jet axis and particles, and leaves the jet. 79
If the liquid wets the solid particles completely, the
particles are immersed in the liquid 'spontaneously'
and without creating a surface depression at the
interface. The stripped particles travel two to three
times as far as the gas jet and could hit the bottom of
the ladle with vertical injection and deeply immersed
injection lances.8o
At low flowrates, coarse particles will penetrate the
gas/liquid interface if they are large, easily wetted, or
moving quickly; small, slow, non-wetted particles
will stick to the gas/liquid interface. At higher
flowrates, the inertial forces dominate over the
surface forces, so that particles always penetrate into
the liquid. Fine particles at high loading form a gas-
particle-liq uid jet.
The momentum flux of the particles is much larger
than that of the gas, so the injection depth is
determined by the balance of governing forces. Engh
et al. simply equated the buoyancy of the liquid
displaced by the solid with the momentum flowrate
of the particles,81 and this has been confirmed with
model experiments.8o Farias and Irons,79 by balanc-
ing the momentum of the jet and its buoyancy, have
confirmed measured penetration depths.
Stripping is observed when the liquid wets the
solid particles. When there is no wetting,80 the
particles remain entrapped in the gas bubble. If the
International Materials Reviews 1988 Vol. 33 NO.2
particles remain partially entrapped in gas, the
observed penetration depth is smaller than calcu-
lated. To obtain maximum penetration, the contact
angle should be as low as possible.
The above force balance of Engh et al. adequately
describes water modelling data of particle penetra-
tion into water after having been blown on to the
surface of the water.82
The rising solid particles might vaporise (Mg),
melt and dissolve (Ca, CaC2, CaSi), and then
vaporise (Ca). They might also coagulate or. coalesce,
thus decreasing their phase boundary area towards
the metal bath. The rising particles should react
completely before they coagulate, coalesce, or join
with the top slag, otherwise their reaction potential is
not fully exploited during their rise through the bath.
However, this might create a not unfavourable
situation if it is possible for the top slag to be
dispersed back into the bath, although the top slag
usually has a different composition to that of the
injected particles. The probability that the injected
particles react completely during their dwell time in
the metal bath increases if they are small and in a
liquid state. Top slag and particles tend to
accumulate away from the breakthrough eye.
There are several reaction zones: 83
(i) the jet zone directly in front of the nozzle,
where the three phase dispersion metal-solid
particles-gas is formed
(ii) the bubble plume, where bubbles, solid and/or
partially molten or reacted particles, and steel
melt rise and react in a turbulent manner;
some of the particles might still be present
inside the gas bubbles
(iii) breakthrough zone at the melt surface, where
there is also reaction with air (if not
excluded); here, particles and/or reaction
products are absorbed into the top slag, and
gas is ejected into the atmosphere
(iv) top slag with phase boundary in contact with
the metal (trapping of reaction products, bulk
reaction slag/metal at phase boundary, and/or
emulsification back into the metal) and
towards the atmosphere (pick-up of N2 and
O2, and transferring them to the metal,
influencing the oxygen potential of the slag)
(v) metal/lining phase boundary with side reac-
tions, 'for example, reduction of lining oxides.
Emulsification, dispersion formation,20 and degree
and time of mixing in all the phases (metal, top slag,
dispersed slag droplets either produced from injected
particles or stripped off the top slag) are important
parameters. If there is poor mixing, then small
driving forces between metal and slag (top and/or
droplets) cause small mass fluxes, long treatment
times, poor yield, and hence high specific consump-
tions of the injected material.
It has been found in model experiments that the
rate of reaction of Na2C03 particles with an 0·1 N
HCI solution is much faster when the lance tip is
immersed at half the bath depth than at three-
quarters of the bath depth. In the latter case, a ring
of Na2C03 particles accumulated around the lance
tip.sO

Practice of solid injection with gas
This technique is relatively simple in that it only
needs a lance with some auxiliary equipment for
materials handling and storage, a powder dispenser,
and a collecting system for the dust formed. The
optimisation of injection depth, particle size, and size
distribution, as well as composition, quantity and
feed rate, might take some time, given the need to
achieve minimal residual impurities at IKwest cost,
with smooth operation.
High carrier-gas/solid ratios favour jetting
behaviour of the injected material, heavy splashing,
and lengthy injection periods; low ratios lead to
increased temperature losses. Pressure variations in
the supply line cause splashing and nozzle blocking.
Splashing at the surface of the bubble plume and
reaction between air and steel can be controlled by
shielding the injection lance with a refractory tube.
Its inner diameter should be somewhat greater than
the bubble plume on breakthrough and it is
immersed someway into the liquid metal. 84 This
immersed tube has already been described in the
section on stirring patterns.
Nozzle clogging is explained by the following
mechanism. In the bubbling regime of bubble
formation, there ·are back attacks of the liquid
against the nozzle mouth after bubble detach-
ment. 85-88 During the interval between the time one
bubble leaves and the next one forms, liquid surges in
to fill the volume formerly occupied by the gas. The
momentum of the liquid is directed into the nozzle.
When the moving liquid contacts the mouth of the
nozzle, droplets are ejected into the nozzle, where
they can solidify at the nozzle wall as droplets or as a
coating. The penetration of the liquid into the nozzle
causes the pressure in the gas supply train to ·rise.
Penetration is greatest into vertically oriented
nozzles. The ratio of the maximum penetration depth
lmax to the inner diameter di of the nozzle, given by
lmaJdi = 4·44 X 10-3di Fr-1/2 • (22)
where Fr is the Froude number, could be corre-
lated86 with a modified Froude number
Fr = pgu;as (pg)2 . (23)
P1gdi P1
The nozzle might De clogged, accretions might form
within the nozzle or at the nozzle exit, and the
refractory wear might increase.
Recently,89 it has been shown that metal penetra-
tion in the nozzle is controlled by the jet Froude
number F,r', where Fr' = Fr(p1/pg)2, and not by the
gas velOCIty or Mach number alone. A jet Froude
number of 2400-2500 is required at standard
conditions to prevent any penetration of molten steel
into the nozzle. Accordingly, depending on the inner
diameter of the nozzle, it may not be sufficient to
inject gases at sonic or supersonic velocities to
prevent metal penetration.
The frequency of back attacks decreases with
increasing supply pressure of the injected gas. With
double walled tuyeres, these back attacks are less
frequent at the same gas supply pressure. They
decrease with increasing difference between central
Lange Secondary steelmaking processes 71
and shrouding gas pressure and disappear if the
shrouding gas pressure reaches 7-8 bar.90 The
supply pressure of the central gas is less than that of
the shrouding gas.
Powder injection decreases penetration depth.
When the powder flow stops, then the chilling effect
stops and the plug formed can remelt, .resulting in a
sudden expulsion of gas and particles previously held
back in the conveying line. Jetting reduces the
probability of clogging because no liquid penetrates
the nozzle.91
In the conveying line, the particles move more
slowly than the gas and, at lower gas velocities, the
particles attain a slip velocity close to that of single
particles in an infinite medium. With increasing gas
velocity, however, they have no time to accelerate to
that slip velocity. The force to accelerate the partiCles
comes from an increased pressure drop in the
conveying line.
For larger sized particles, it is found80.81 that the
particle velocity at the lance tip is almost half that of
the gas velocity. It has been shown 79 that the
velocity ratio reached depends on the extent to which
the gas can accelerate the particles.
The addition of some gas producing particles, such
as CaC03, is beneficial. When they hit the hot steel
gas is suddenly produced, breaking up the bubble~
with their particle loads and creating more turbu-
lence within the bath. The reactivity of the gas so
produced should suit the desired thermodynamics,
for example, oxidising CO2 is suitable for dephos-
phorisation but not for steel desulphurisation.
INJECTION OF SOLID CALCIUM
BEARING PARTICLES WITH CARRIER
GAS
Thermodynamics and kinetics
Calcium and its alloys have become very popular in
ladle metallurgy because of their favourable thermo-
dynamical and kinetic properties. The injection
treatment reduces the oxygen and sulphur content of
steel, modifies the non-metallic inclusions and
improves steel cleanness. The process was dev~loped
at Thyssen- Niederrhein, hence the name TN process .
The materials used are listed in Table 12. Besides
al~oys such as CaSi, CaC2, and CaCN 2' mixtures
wIth CaO and of Mg with lime and fluorspar are also
used. The following figures are given for the powder
size:93
CaSi: 0-0·6 mm and 0-1 mm
CaC2: 0·1-0'6 mm
CaMg: 0'1-1·5 mm.
Also available are granules of metallic calcium with
the following compositions:
98'5%Ca: 0'5%Mg (max.), 0'45%AI (max.),
0·015%N (max.)
80-98·5%Ca: 0·5-20%Mg, 0·45%AI (max.),
0·015%N (max.)
The price ratio of CaSi to 80CaO-20CaF 2 is 5: 1
(Ref. 94).
T~e v~po~r pressure of calcium is high, making its
applIcatIon In ladle metallurgy difficult, but at the
International Materials Reviews 1988 Vol. 33 NO.2
72 Lange Secondary steelmaking processes
Table 12 Desulphurisation agents for powder injection
Desulphurisation agent Composition
SiCa 62%Si, O'8%AI (30%Ca)
Calcium carbide 80%CaC2, 15%CaO (50%Ca)
Calcium cyanamide 55%CaCN2, 33%CaO, 12%C (28%Ca)
Mg (CaO/CaF2) 5-20%Mg
CaO-CaF2 90%CaO, 10%CaF2
CaO-AI203 50%CaO,50%AI203
CaO-AI203-Ca F2 70%CaO, 20%AI203, 10%CaF2
same time offering unique possibilities. Calcium has
a melting point of 850°C and, a boiling point of
1490°C. Its vapour pressure at 1600°C is reported to
lie between 1·6 and 3·7 bar, depending on the
literature source. It is clear, however, that at
steelmaking temperatures a high vapour pressure of
calcium can be expected. The bath depth at which
the boiling of calcium is suppressed depends on the
steel temperature as well as the steel composition.
Calcium solubility in pure iron is 300 ppm at a
total argon pressure of 10 bar above the melt95 or
160 ppm at Pea = 1 bar.10 It is increased by, for
example, the addition of C, Si, Al and lli, and is
decreased by Cr. Therefore, a definite, but small,
solubility of calcium in liquid steel has to be
expected. Values between 40 and 80 ppm are
reported for liquid steel. 93 Such a solubility is
favourable, because it allows retention, even after
treatment, of some dissolved calcium in the steel melt
to ensure inclusion shape control until the steel is
solidified. The solubility of calcium in solid steel is
less than 1 ppm.96,97 Therefore one has to assume
that practically all the calcium analysed in solidified
steel is present in the form of oxides or sulphides. ' Calcium forms with Al203 spherical low melting
The free enthalpies J1GO of formation of oxides and
sulphides of calcium and magnesium show that both
elements have a very strong affinity (Ca more so than
Mg) towards both oxygen and sulphur. This explains
their popularity as deoxidisers and desulphurisers.
Since both oxides are more stable than the sulphides,
both elements will react with both oxygen and
sulphur dissolved in steel.
Dissolved oxygen competes with sulphur for
calcium and impedes th~ removal of sulphur.
rherefore oxygen has to be removed before the
sulphur, with additions of aluminium, for example.
Calcium and magnesium not only react with oxygen
(and sulphur) dissolved in steel but also with oxygen
(and sulphur) bound weakly in MnO, (MnS), or
Si02, and these compounds are -therefore reduced
either from inclusions in the steel or from top slag
containing such compounds.
Metallic calcium and/or magnesium should' be
injected as deeply as possible into the melt, so as to
provide as long a reaction time as possible. Both
metals melt and/or vaporise, and then dissolve in the
steel, any surplus rising as vapour to the bath
surface. The vapour bubbles should ideally be
consumed by the reaction with oxygen and sulphur
before they reach the bath surface. The bubble size
during its rise is thought to be determined by two
opposing effects: an increase in size due to decreasing
International Materials Reviews 1988 Vol. 33 NO.2
(Ref. 92)
Amount
injected, Amount of agent for
kg t-1 115/ So = 0·90, kg t-1
2-4·5 3·87
1-3 2·32
0·4-1 (4.22)
1-3 2·2
3-6 3
1-5 4
1-5 3
ferrostatic head and a decrease in size because of
consumption due to reaction.
As far as calcium bearing material is concerned, it
is usually assumed that the particles are heated
quickly, that carbon and silicon are dissolved in the
metal, and that calcium, at least at a certain bath
height, evaporates and rises as bubbles through the
steel melt, as above. Because. of this gas formation, it
is not necessary to use extremely fine powders. Large
particles will break up, provided that their tempera-
ture increase after injection is fast enough to create
enough vapour pressure for bursting before the
particles reach the bath surface.
Modification of inclusions
The attractiveness of calcium lies in its ability to
modify the oxides and sulphides left in the solidified
steel.
Aluminium is a widely used strong deoxidiser; its
deoxidation products are usually high melting point
clusters, which produce planar inclusions during hot
rolling, thereby degrading the mechanical properties
of the steel.
point calcium aluminates with changing CaO-AI203
compositions. It is clear from the binary CaO-AI203
phase diagram that the melting points of the calcium
aluminates decrease up to about 50% CaO, after
which they increase again. The liquid calcium
aluminates coalesce and rise more easily than the
high melting point alumina inclusions. The few small
ones left in the solidified steel are not deformed on
rolling, as for MnS and Al203 inclusions, but remain
globular, producing a high isotropy of mechanical
properties of steel in longitudinal, transverse, and
through-thickness directions, and giving improved
toughness properties. This inclusion modification
effectively helps to decrease the probability of nozzle
clogging, since the liquid calcium aluminates have no
tendency to build up on the nozzle surface.
Calcium also changes sulphide inclusions, with all
sulphides in aluminium killed steel being transformed
into globular inclusions when the calcium left from
deoxidation at the beginning of the solidification is
sufficient to react with more than 40% of the
dissolved sulphur. 19 Manganese sulphides with 3-
10%Ca are not deformed during hot working, so
they no longer form planar inclusions. Higher
calcium levels in the sulphides increase their melting
point, causing them to precipitate earlier on
solidification as a finer dispersion, decreasing
centreline segregation of the sulphur. 96

liquid Inclusions 40
50
30
40
20
E calcium in the melt. Injection with gas aggravates the
a.
a.
,.
b 30 10
u
ro
20
10
solid inclusions
o Silicon and carbon pick-up can limit the use of CaSI
-3
[AlJ,10 °10
19 Possibilities of transformation of alumina
clusters by calcium in AI killed steels
(Ref. 19)
The injection of large quantities of CaO-(20-
2S%)CaF z powder modifies alumina inclusions into
calcium aluminates surrounded by an outer layer of
sulphides. When this happens, it is an indication that
the outer layer has precipitated later, using the
primary alumina tes as nuclei. . .
Calcium additions, however, modIfy sulphIdes
better than basic slag injections.19 CaSi or CaSi-
containing powders result in a complete modification
of MnS to calcium containing sulphides and duplex
oxides which are almost globular. Elongated MnS
inclusi~ns remain in the steel for all other variants.
For inclusion shape modification, calcium should
be present in the right proportion. In Fig. 19 are
shown the total calcium contents which are necessary
to produce liquid inclusions in aluminium killed ste.el
for various levels of aluminium and total oxygen In
liquid steel. For shop practices, the follo~ing figures
are given: if there is not enough calcIum (below
0·4 kg t -1 (of steel)), the alumina is no~ completely
modified and molten; too much calcIum (above
1 kg t - 1 ( of steel)) produces high melting point
calcium aluminates in the solid state which are not
easily removed.93 For the formation of l~w ~elting
point calcium aluminates the Cal Al ratIo In steel
should exceed 0·14 (Ref. 98). For inclusion shape
control only, 0·S-0·7 kg (CaSi) t-1 are used.99 No
liquid calcium aluminates are possible at such .s
levels where all the calcium goes to form CaS, leaving
none for calcium aluminate formation.
Limitations of calcium injection
Calcium bubbles can still be large when they reach
the steel surface, if the calcium is not injected at the
critical depth to ensure proper and complete reaction
. before the bubbles reach the surface. At the surface,
Lange Secondary steelmaking processes 73
these bubbles ignite, expose the steel to the
atmosphere and produce appre~iable a~ounts of
smoke, which consists of fine partIcles of hme.
A singly located calcium source does not lead
easily to an even distribution of calcium, but r~th~r
to an upwelling plume of calcium drops, first hqUld
but then rapidly vaporised, which will decr~ase the
residence and reacting time and thus the effiCIencyof
situation with bubbles, and also accelerates the
plume. .
Considerable safety precautIons are necessary
when storing and handling CaCz. Wet CaCz
produces acetylene, while wet CaSi produces
hydrogen.
Pick-up of hydrogen and nitrog~n ar~ probl~ms
with hydrogen originating from mOlstur~ I~ ~he hme
and in the atmosphere. It can be mInImIsed by
careful drying of reagents. Nitrogen originates from
the atmosphere, and steel with very low oxygen and
sulphur levels is very sensitive to nitrogenisation:
and CaC2 in certain steels.
Calcium is extremely reactive towards oxygen from
steel, slag, lining of ladle and injection lance, and
atmosphere. It must therefore be added to steel
under carefully controlled conditions to be effective.
Primary furnace slag is readily reduced, (e.g. MnO,
CrZ03, P20S)·
INJECTION OF MAGNESIUM BEARING
PARTICLES OR RARE EARTH METALS
Despite its high affinity towards oxygen and sulphur,
no general acceptance exists for the use of
magnesium in secondary steelmaking. It~ l?ain u~e is
in desulphurising hot metal: 100 When InJecte? Into
steel, magnesium evaporates, forms bubbles, stIrS the
bath vigorously, combines with oxygen and sulphur,
and rises to the bath surface. To reduce the violence
of the evaporation reaction of magnesium reagents,
they must be injected at a slow rate and/or with some
kind of passivative or diluent additions, for example
in the form of salt-coated magnesium granules or
70%lime-30%Mg and SO%(lime + Alz03)-SO%Mg
powders. The salt coating is usually based on C~Clz
and is hygroscopic. The injection of magneSIum
powder needs careful observation of the heat balance
at the nozzle, since the heat of vaporisation of the
powder might freeze the metal near the nozzle.
Magnesium forms high melting aluminate spinel_~
with alumina inclusions, which can be as harmful as
alumina inclusions with respect to the mechanical
properties of steel products.96 The solubility of
magnesium in iron at 1600°C lies around 1 wt-%; the
elements C, lli, and Al increase that solubility, Cr
reduces it, and Si has no effect.101
Rare earth metals can be used for· desulphurisa-
tion. In this case, the steel should be fully killed to
take full advantage of these expensive agents. It is
better to use them for sulphide inclusion modification
since they allow complete sulphide shape control and
form globular and non-deformable sulphides and
oxysulphides. But the problem of nozzle blockage
and cost has so far prevented their widespread use. A
International Materials Reviews 1988 Vol. 33 No.2
 vacuum, gives about the same yield, but is cheaper
with respect to both installation and running costs
(Fig. 20).
75 Surface injection gives low convective velocities
~
--..
0
0
fLZ3S01 and slow mixing as compared with stirring by
a" 50 bubbling and/or deep injection. To prevent entrain-
..J
llJ
ment of slag, injection should be carried out in the
>- ~ breakthrough eye above the porous plug and the
bubbling rate properly adjusted. 27
25 The vigorous intermixing of an (oxidising) top slag
~ addition during purging in ladle
with the bath and alloying element in the break-
IZZJ addition during vacuum degassing
through eye can be minimised by the lowering of a
o
refractory lined cylinder into the liquid steel just at
100 the position where the bubble plume creates an

-
• _tot
75
--..•..
0
0
a when exposed to air .
..J 50
llJ
> .501
25
ladle Injection
0
c Si AI B Se
ALLOYING ELEMENT
20 Comparison of different alloying techniques
(Ref. 103)
recent overview is ·available.102 Rare earth metal
inclusions are relatively heavy and therefore remain
more easly suspended in the melt.
ALLOYING AND GAS INJECTION
Alloying can be done in several ways, for example,
during tapping, in the ladle by simply dropping the
material on the surface, and with a carrier gas. The
alloying with elements having a high affinity towards
oxygen should not be made in the presence of either
an oxidising atmosphere or an oxidising slag if high
yields are to be expected. This can be seen in Fig. 20.
The loss of alloying elements is due to uncontrollable
oxidation by carried over refining slag, aggravated
by the subsequent stirring of the melt and any
thermodynamically unstable lining oxide, such as, for
example, Si02. This oxidation does not allow the
narrow limits of element specification to be achieved
which are essential for product quality.
The dissolution and homogenisation of the
alloying additions are enhanced by stirring and small
particle sizes. A temporary coating of the solid with
slag will retard dissolution.
Alloying consumes heat for melting, and this heat
is taken either from some superheat given to the steel
in the converter or from a separate heat source which
can be a chemical one (V0 D, A0 D) or electric arc
heating (ladle furnace, ASEA-SKF, Finkl-Moore).
Manganese and chromium show the greatest cooling
effect of the commonly used alloying elements,78 and
data for estimating temperature changes due to
alloying, deoxidation, and reoxidation is avail-
able.104 Alloying by injection, instead of in a
opening in the top slag. The inert gas escaping at the
breakthrough eye decreases the' partial pressure of
oxygen and nitrogen within the cylinder dipped into
the steel, and hence diminishes the reactions of steel
WIRE FEEDING AND INJECTION OF
ALUMINIUM PROJECTILES
Wire feeding involves the feeding of powdered \
reagents encased in a metal sheath or supplied
directly as a wire product into the ladle. It allows
precise metered additions of small amounts of
reagent for aluminium trimming and calcium
additions for inclusion shape control and for the
prevention of nozzle clogging. Two advantages are
that there is no need for injection lances (as long as
the wire is not directed by lances!) and that the
added material is separate from the stirring agent.
The reduction in turbulence compared with pneu-
matic injection gives lower heat losses and lessens the
chance of oxygen and nitrogen pick-up from the
atmosphere.
During the injection of, for example, an aluminium
wire into a steel bath, heat transfer is important.
Owing to the heat transfer from hot steel to the cold
wire, a steel shell freezes around the wire which
grows towards a maximum thickness depending on
the process (feeding rate,' melt stirring, temperature
difference) and physical (heat transfer coefficient,
heat conductivity) parameters. Within the steel shell
formed, the aluminium is heated and melted, and as
the steel shell melts away, it is bent by loss of
strength and by the buoyancy of the aluminium.
Liquid aluminium is distributed by the feeding
action, by rotation of the wire, and by the stirring
action of the gas injected from the bottom of the
ladle. With increasing feeding rate, the heat flux into
the wire increases, the thickness of the steel layer
decreases, but the depth of injection increases.
When wires containing calcium compounds or
metallic calcium are fed to such depths that the
vaporisation of calcium is suppressed and liquid
calcium drops are formed, then the absence of gas
allows a slower rising speed of the droplets and
therefore a longer reaction time of the upward
floating droplets. This advantage is lost as soon as
they reach bath depths where vaporisation starts.
The slower rising speed of the calcium drops can be
taken advantage of, however, only if a further
mechanism for calcium distribution throughout the

International Materials Reviews 1988 Vol. 33 NO.2


melt is available. The snaking of wire injection (if
there is any) should help in distributing calcium.-
Surface tension, however, probably establishes large
sized calcium droplets.
The injection of aluminium projectiles has been
investigated.los-lo7 The problem is to dissolve and
to disperse the aluminium completely before any
undissolved aluminium returns to the steel surface
owing to its low density.
REACTIONS OF SECONDARY
STEELMAKING
DESULPHURISATION
Desulphurisation methods
The demand for improving desulphurization has
arisen for two reasons: the dwindling availability of
coke low in sulphur increases sulphur input into the
blast furnace and the increasing demand for
decreased sulphur levels in steel products requires
lower sulphur residuals in steel. There are two
mechanisms available for desulphurisation:
(i) reaction between S and a desulphurising
element both dissolved in steel, precipitation of
sulphides within the metal phase, and their
subsequent removal from steel
(ii) reaction at the boundary with another phase
either solid (e.g. lime) or liquid (e.g. basic slag)
and transfer of sulphur from the metal to the
slag by an electrochemical exchange reaction
S+(02-) = (S2-)+Q . (24)
in which the sulphur exchanges two electrons
with oxygen, bringing one oxygen ion from
slag to the metal as atomic oxygen; the oxygen
ion in the slag acts as electron donor, and,
when the oxygen potential is raised, iron enters
the slag as oxide, which is very sensitive to the
oxygen potential of the gases above the slag.
At steelmaking temperatures, the affinity of elements
towards sulphur decreases in the order cerium,
calcium, lanthanum, magnesium, and manganese.
Further main factors influencing desulphurisation are
oxygen activity in the slag and metal, amount and
composition of top slag and desulphurising agent,
contact area between reagents, and metal tempera-
ture. Therefore successful desulphurisation depends
on the following prerequisites: low oxygeq potential;
basic lining; sufficient stirring intensity to promote
metaljdesulphurising agent emulsification; and suffi-
ciently high temperature to obtain melt and liquid
desulphurising agent of low viscosity.
Because of the highly reducing conditions and the
possibility of using a slag of high basicity, the blast
furnace can be an excellent desulphuriser. But it is
more economical to run the blast furnace with a not
too basic slag, tolerating higher sulphur levels in hot
metal, and to desulphurise externally. Since the
activity coefficient of sulphur in hot metal is much
greater than in molten steel, it is better to remove
sulphur as far as possible from hot metal and not
from steel. For very low sulphur levels, however, a
steel desulphurisation step is indispensable.
Lange Secondary steelmaking processes 75
Because of the high oxygen potential in a BOF,
usually only 50% of the sulphur of a BOF heat can
be removed. The adding of magnesia to steelmaking
slags for extending lining life de,creases the sulphur
partition ratio. A summary of steel desulphurisation
processes, together with advantages and limitations,
is given in Table 13.
For the desulphurisation of steel melts, two types
of powders are used. The first type, e.g. CaSi, CaC2,
CaAI, rare earth metals, and Mg, causes precipita-
tion reactions, and the other type, e.g. CaO, CaO-
CaF 2' and CaO-AI203-CaF 2' causes exchange
reactions. While the powders of the first type are
usually injected, the powders of the second type,
although also injected, may be simply added to the
top of the steel bath.
In all cases, a thorough deoxidation of the steel
and continuous prevention of any reoxidation is a
prior condition for success. Other prerequisites are
thorough dispersion of desulphurising agents in the
steel melt, and promotion of turbulence by
providing sufficiently large quantities of stirring
energy, usually via gas injection.
With top slag, the success of desulphurisation
depends on the degree of liquefaction, dispersion,
deoxidation, and lime activity of the top slag.
Usually a compensating heating source is necessary
because of the extended treatment times and the use
of large amounts of stirring gas. Arc heating
promotes a liquid slag of high basicity.
Desulphurisation by precipitation
reactions
CaSi is a popular desulphuriser, but expensive. For
steel qualities where the increase in Si cannot be
tolerated, CaC2 may be injected, provided the
increase in C is acceptable. As long as the oxygen
activity of the steel melt can be properly controlled to
sufficiently low values, CaSi- and CaO-based
powders, whether deeply injected or put on top of
the melt but in the molten state, produce equal
degrees of desulphurisation, as can be seen, for
example, in Fig. 21, where the same degree of
sulphur removal is reached with 4 kg CaSi per tonne
at 100% relative cost or with 6 kg (SO%CaO + 20%
CaF 2) per tonne at 40% relative cost. For S less than
10 ppm and/or inclusion shape modification, CaSi is
usually used, even after CaO-based slag treatment.
With BOF slag removed with vacuum suction,
lime addition to the remaining slag, deoxidation with
aluminium, and strong gas stirring, it is possible to
reach 6 ppm .s without powder injection. CaSi
powder is only injected for sulphide shape control.108
Desulphurisation by exchange reactions
Synthetic lime-based slags for desulphurisation have
become important for steel desulphurisation. They
are based on lime-alumina or lime-fluorspar and are
used in conjunction with reducing agents like AI,
CaC2, or CaSi. Slags based on lime-silica are not
recommended for desulphurisation.
The fluidity of such slags is important, the fluidity
decreasing with increasing CaO content, giving a
reduction in the rate of desulphurisation. The
International Materials Reviews 1988 Vol. 33 NO.2
76 Lange Secondary steelmaking processes

Table 13 Steel desulphurisation processes* in production use (Ref. 97)

Type and mode

of treatment Basic equipment Reagent Advantages Disadvantages Country of use

Direct production in Primary furnace Lime, powdered No special equipment, Limited ability for low Worldwide
BOF. Q-BOP, or EF fluxes, (tuyere inexpensive, rimming sulphur contents,
injection in Q-BOP) steels ca n be treated vessel productivity
decreased to reach
lower sulphur content
Teeming ladle
Tap stream Ladle Synthetic slags, fluxes No special equipment, Must avoid furnace Worldwide, most
relatively inexpensive slag carryover, limited prevalent
ability to reach very
low sulphur contents,
some fuming
Ladle injection Lances, dispensers Lime, fluxes, Ca, Controlled Must avoid furnace Worldwide, used
Ca-Si, Mg-lime, desulphurisation to slag carryover, primarily for higher
carbide low levels auxiliary equipment quality steels
required, some
fuming, temperature
loss, expensive
Wire feeding Wire feeder Ca, Ca-Si Controlled Must avoid furnace Several shops
desulphurisation, slag carryover, worldwide
integration with other expensive per unit of
processes required, sulphur removed
morphology control
Ladle-furnace Heating unit, stirring, Synthetic slags, fl uxes Ultimate in control, Must avoid furnace Many shops
systems and, in some cases, can achieve very low slag carryover, higher worldwide
vacuum capability sulphur contents installation cost,
prolonged processing
cycles, high operating
cost
Multiple-vessel treatment
Double ladle Second ladle Synthetic slags, fluxes Effective treatment, High tap temperature, Few shops, special
standard processing second ladle, crane heats only
time required, fuming,
variable temperature
loss
AOD AOD vessel Synthetic slags, fluxes Excellent control, Higher cost, second Many shops
ability to reheat vessel, limited heat worldwide
size

* AOD, argon-oxygen decarburisation; BOF, basic oxygen furnace; EF, electric furnace; Q-BOP = OBM process.

addition of fluorspar, while gIvIng a high slag results3 with slags contaInIng CaO and 20-80%
fluidity, also increases slag attack of the ladle lining. CaF 2. The sulphur partition (S)jS decreases mono-
Figure 7 shows the range of slags used for tonically with increasing alumina and silica contents
desulphurization in the system CaO-AI203-Si02• in the slag, and can be estimated by
They are low in Si02 and lime saturated. In this (S)jS = 1260-25(% AI203)-75(% Si02) (25)
range, the equilibrium partition coefficients of
sulphur and the activities of lime are at a maximum On the other hand, both oxides accelerate the
and the activities of alumina and silica low, as can be melting of CaO and where there is already a liquid,
seen in Figs. 22-24. Figure 22 is an extension by lime saturated slag present, alumina and silica inhibit
model calculations of literature results for three- or desulphurisation. If there is not much lime in
four-component slags to the system CaO-AI203- solution, the fluxing action of alumina and silica
Si02-5MgO. The composition range leading to indirectly enhances desulphurisation by bringing
sulphur partition ratios of 1000 are at the lime lime into a liquid state.
saturation line and at low silica levels. Increasing
silica and alumina levels decrease sulphur partition. Influence of oxygen potential
This retarding influence of silica is corroborated by The reaction
S+(CaO) = (CaS)+Q . (26)
Table 14 Oxygen and sulphur activities in steel can only work satisfactorily at low levels of oxygen
activity in the steel. With readily available data,110
BCaD = 1, BCaD = 1, one obtains
BCaS =1 BCaS = 0-1
S, ppm S, ppm S, ppm S, ppm
K = aoaCaS(asaCaO)-l = 2·16 x 10-2 at 1800 K
Q, ppm 1800 K 1900 K 1800 K 1900 K 2
= 3·06 X 10- at 1900 K
100 4600 3300 460 330
50 2300 1600 231 160 or, with as = %S and ao = %0, Table 14 is
10 460 330 46 33 obtained. This table demonstrates clearly that low S
5 231 160 23 16 levels are only possible at low Q contents.

International Materials Reviews 1988 Vol. 33 No.2

 Lange Secondary steelmaking processes 77

Si02 -- a (caO)J wt-ok

100 ----a(Al2~),wt-"

-
I \ \ \\ \\ \\ \ \'\ \\
0 A
0 80
a~ (4ppm
'0
If)

"
If)
60

-
<l
0
0 40

20
20

2 3 4 5 6 90
CaO
m, kg t-1
CaO 10 20 30
21 Degree of desulphurisation as function of
amount of injected powder and oxygen
activity of steel before injection (Ref. 94) 23 Activities of CaO and AI203 (wt-%) in A1203-
CaO-Si02 system at 1600°C (Ref. 109)

The oxygen activity is influenced by the Q-AI-

ladle. The oxygen potential is easily increased by the
Al203 (and/or Q-Si-Si02) equilibrium. Therefore
atmosphere, refining slag carried over, oxi?ised steel
one can also write
adhering to the ladle wall from the prevIous. h~at,
3S + 3(CaO) + 2AI = 3(CaS) + (AI203) . (27) less stable deoxidation products, or the lInIng.
Resulphurisation is likely if the top slag is ?eing
indicating that Al is used to remove the oxygen from
oxidised continuously from the above-mentIoned
the sulphur exchange reaction. For good ?e~ul-
sources. The top slag must have and keep a high
phurisation, the activities of lime an~ alumInIum
basicity and a low oxygen potential: The o~idi~ing
should be high, those of CaS and alumIna should b.e
potential of the top slag can be descnbed by ItS Iron
low. Nearly all these prerequisites can be fulfilled If
and manganese oxide contents.
there is a liquid slag saturated with lime and with a
The slag is gradually reduced through an exchange
low oxygen potential. .
reaction with the steel,
The high basicity and high lime activity are eaSIly
decreased by Si02 formation, for example, from 3(FeO) + 2AI = (AI203) + 3Fe . (28)
deoxidation with silicon or from an acid lining of the
through which its oxygen activity is decreased. At the
same time, lime is gradually dissolved increasing the
activity of lime. Both reactions improve desul-
°/oCaO
phurisation, but need some time. Therefore real care
55 45
(a)

7
5
.J}.
01'fJo 0u;.
o~8~ 10~

(b)
,
65

75

0
01'fJ
~o 85
70 ,'r..~o
~ ',30
:>-' .~~ -<1/. "
95 80 .J.". ~ '. ~<3 .
0 10 20 30 C'~o', - -', ~~_', 10
OfoAl203 90 ·~o . ~
~ C'~>., ~o",
a Ls = (%5)/[%5]; bas CaO . ~~. 1 w \

22 Equilibrium partition of sulphur and silicon CaO 10 20 30 40 50 60 70~80 90 Al20:3

AL203, wt-Ofo
between aluminium containing steel
(aAI = 0·03) and CaO-AI203-Si02-5MgO slag at 24 Activity of Si02 (wt-%) in AI203-CaO-Si02
1625°C (Ref. 19) system at 1600°C (Ref. 109)

International Materials Reviews 1988 Vol. 33 NO.2

78 Lange Secondary steelmaking processes

systems permit the formation of very fine emulsions,

800 and it, is possible always to produce new particles to
be dispersed. Solid-liquid systems, however, disperse
en 600
the same solid particles over and over again, if no
~
••...• new ones are continuously fed. But this means
en
- 400
increased consumption of solid material and
decreased yield.
Because of its high melting point, far above
200
2000 K, CaD alone cannot be melted. Fluxes are
necessary, such as, for example, aluminium oxide
(and fluorspar). Therefore the state of the slag
B nCaO + °CaF2
becomes crucial for "the successful removal of
nSi02 + nAI203
sulphur, depending on the oxidation state of the slag
and on the dissolution of lime.
25 Sulphur partition as function of oxygen For the same CaO injection process, smaller CaO
activity and basicity (Ref. 38) particles and a better mixing capacity improve
desulphurisation. Good desulphurisation results in
A0 D, VAD, and ladle furnaces show the importance
should be taken in mInImIsIng the slag carryover of intimate emulsification of slag and metal and of a
and the influence of the lining and atmosphere. In liquid slag of high basicity. Therefore attempts must
this respect, the oxygen fluxes associated with the be made to ensure that injected lime based
various sources should be estimated in order to know desulphurisers melt before they reach the steel
their relative importance. surface, and, if not, that at least the top slag is melted
Figure 25 demonstrates at least two points: with a chance of being redispersed into the metal.
desulphurisation is remarkable only at low oxygen Sulphur transfers from metal to slag through a
activities, and at only low oxygen activities can a phase boundary reaction of the type given in
high lime and/or fluorspar ratio develop its beneficial equation (26). The rate determining step can be the
influence. transport in one of two phases, metal or slag, or the
The calculated equilibrium sulphur contents in phase boundary reaction, or even a combination of
Table 15 are very low. these elementary steps. Therefore stirring of either
It might be argued that, as for oxygen, a the bulk phases and/or the interface has a great
distinction should be made for sulphur between total influence in addition to the emulsification and
sulphur, dissolved sulphur, and sulphur contained in liquefaction of the phases involved.
residual non-metallic inclusions if the sulphur The desulphurising capacity of the top slag must
dissolved in steel has to be known for making be at least as good as that of the injected
thermodynamic calculations. desulphurising agents rising through the bath. If this
is not the case, resulphurisation will occur

Importance of state of desulphurising (CaS)+Q = (CaO)+S . (29)

agent
To obtain good desulphurisation, the lime should be
in a kinetically favourable (i.e. liquid) condition. The
liquid state allows a higher conversion rate than a
solid-liq uid reaction, where only the surface can
react fast, and where the solid bulk can take part
only by slow diffusion. In addition liquid-liquid
Usually any reversion is caused by an increase in the
oxygen potential of the top slag or lime not in molten
state.
At the beginning of a desulphurisation process, the
initial sulphur content, and therefore its chemical
potential, is at the highest. Therefore desulphurisa-
tion can be started with a low priced desulphuriser

Table 15 Values of equilibrium constant K and equilibrium sulphur

content [%Sleq' calculated from reported thermodynamic
values, for interaction of sulphur and desulphurising
additives to form solid sulphides in liquid iron alloys
(Ref. 97)

Reaction Temp., K K [%S]eq' wt-%

Mg(g) + [S] = MgS(s) 1643 1·85 x 104 5·4 X 10-6

1873 4·12x102 2·4x10-3
Ca(l) + [S] = CaS(s) 1643 7·34 x 108 1·4 x 10-10
Ca(g) + [S] = CaS(s) 1873 9·30 x 106 1·0x 10-7
[Ce] + [S] = CeS 1900 2·10 x 105
3[Ce] +4[S] = Ce3S4 1900 1·40 x 1018
2[Ce] +3[S] = Ce2S3 1900 2·50 X 1012
[La] + [S] = LaS 1900 1·00 x 105
2[Ce] +2[0] + [S] = Ce202S 1900 7·70 x 1019
2[La] + 2[0] + [S] = La202S 1900 1-40 x 1021
CaC2(s) + [S] = CaS(s) +2[C] 1643 2·5x10-7
CaO(s) + [S] = CaS(s) + [0] 1643 8'38[0]
1873 40'0[%0]

International Materials Reviews 1988 Vol. 33 NO.2

 Lange Secondary steelmaking processes 79

with an inferior desulphurisation capacity (e.g.

CaO + CaF 2)' After removal of the first part of the
sulphur from the melt, a desulphuriser with higher
affinity towards sulphur, such as calcium, can be
applied to decrease the sulphur level of the metal no refined
further. This selective use of materials having
different sulphur affinities only works if none of the
first part of the sulphur removed from the melt can
-
°I
+oJ
°
treatment

react with the high affinity desulphuriser. Otherwise, ~ refined

the higher sulphur affinity is also imposed on the ladle
~ treatment
reaction products already removed, and some part of Z
W
the high affinity desulphuriser added later will react ~
with previously formed desulphurisation products. Z
o
U
10-3
DEOXIDATION
Z
Deoxidation comprises both the lowering of oxygen w
activity in liquid steel and the decrease of the total t9
oxygen content of the steel. Since some of the >- "
X Liquid"
,
.•....
deoxidation products are dispersed in the steel melt, o
the total oxygen content is higher than the amount of "blind"of v f. m t',
SOC/SOA .•......•...•...•.
dissolved oxygen in equilibrium with the de oxidising
CoO
element. The difference is found in non-metallic 10-4
inclusions. Their net rate of removal determines the
steel cleanness. 10-3 10-2 10-1
The control of activity and total content of oxygen ALUMINIUM CONTENT, wt-o/o
in steel is the main key to the cleanness and quality 26 Equilibria between oxygen and aluminium in
of steel, i.e. the decrease of oxygen activity is a liquid iron at 1600°C in presence of oxide
prerequisite for successful desulphurisation. phases of AI203-CaO system (Ref. 57)
The rate of reactions that decrease oxygen activity
are high, but the rate of removal of small inclusions
is low. Therefore the total oxygen content will be low in steel, the equilibrium content of oxygen dissolved
only if the removal rate is high and the reoxidation in steel is further reduced, as can be seen, for
rate low. example, in Fig. 26.

Lowering of oxygen activity in steel bath Decrease of total oxygen content in steel
The lowering of the oxygen activity is achieved easily The total oxygen content of steel will be at a
and quickly by adding to the steel melt an element minimum if its content of non-metallic inclusions is
with high affinity towards oxygen, like Ca, rare earth at a minimum, although non-metallic inclusions
metals, Mg, AI, Ti, and Si (in order of decreasing comprise oxides, sulphides, oxysulphides, and other
affinity), and/or alloys containing these elements components, such as nitrides or carbides. Since much
initiating the reaction of the following pertains to all non-metallic inclu-
sions, the discussion is not confined to oxides in
xQ+ yMe = (MeyOx) • (30)
particular.
and forming either solid (AI203) or liquid (calcium Some of the aims of ladle metallurgy are as
aluminates, silicates, MnO) or gaseous (CO) oxides. follows:
Condensed oxides form inclusions and/or slag;
(i) to decrease as far as possible the quantity of
gaseous oxides leave only blowholes in the steel.
non-metallic inclusions
Inclusions in liquid steel have to be removed by
(ii) to distribute as evenly as possible the
agglomeration, coagulation, and separation. Mostly,
remaining non-metallic inclusions
precipitation deoxidation with silicon and/or
(iii) to provide inclusions with compositions that
aluminium is utilised, with calcium being used to
·assure beneficial mechanical properties.
attain very low oxygen activities, total oxygen
contents below 20 ppm, and/or inclusion shape Inclusions which elongate during hot working
control. decrease the ductility and impact properties of steel,
From thermodynamics low activity of deoxidation especially in directions transverse to the hot rolling
product, high activity of deoxidiser, and low direction. If the inclusions remain globular (e.g. after
temperature are recommended to obtain low oxygen calcium additions), then the mechanical properties of
activities in steel. Low activities of the deoxidation the steel are about the same in every direction.
product are obtained by, for example, deoxidation The cast product contains fine inclusions (1-5 Jlm)
with manganese and silicon or aluminium and and inclusion clusters (> 30 )lm). Inclusions larger
calcium, where the activities of MnO and Si02 or than 100 Jlm in cast steel are usually due to
Al203 and CaO are lowered in the resulting liquid reoxidation or entrainment and/or entrapment from
manganese silicates or calcium aluminates (Fig. 23). slag, refractories, or scums. Such inclusions, even
Therefore, for the same silicon or aluminium content when few in number, give a deterioration in steel

International Materials Reviews 1988 Vol. 33 NO.2

80 Lange Secondary steelmaking processes
quality. The number of inclusions in steel changes
exponentially from about 1014 m - 3 with a particle
diameter of 1 J-lm to about 108 m - 3 for a particle
diameter of 20 J-lm (Ref. 111). Assuming a bound
oxygen content as Al203 of 30 ppm, then an average
particle diameter of 20 J-lmgives about 1010 particles
of this size per tonne of steel. 112
The following parameters influence the removal
rate:
(i) growth of inclusions by diffusion (this can be
neglected in practice) and by agglomeration
and coagulation
(ii) net rise as influenced by surrounding liquid,
by buoyancy, and by flotation with gas
bubbles
(iii) deposition at interfaces (other inclusions,
particles, top slag, lining)
(iv) transfer to other phases, such as liquid top
slag.
Stirring improves the distribution of the deoxidisers,
and the agglomeration and coagulation of precipi-
tated inclusions with each other, with top slag, and
with the lining. Agglomeration or coagulation is
usually considered to be the rate determining step.
Stokes law gives a velocity for a 10 J-lmparticle in
liquid steel of 0·2 mm s -lor even smaller. This is
very small. Steel velocities of the same order are
enough to upset the rise of the particle, and therefore
the motion of such small particles should be
considered as being governed by the motion of the
steel and not by their own buoyancy, which is,
however, still active. Inclusions of this size therefore
remain suspended and move along with the
convective bulk flow of molten steel. Collisions
between inclusions occur, resulting in aggregates,
clusters, or globules. The former are usually a
network of alumina inclusions, and they behave like
a sphere of the same large radius, rising quickly to
the steel surface.
Collisions are differentiated: Stokes collision
occurs because of different rise velocities under the
action of buoyancy; gradient collision occurs with
different velocities of the liquid in which particles and
inclusions are suspended. Injected and/or dispersed
particles, either solid, liquid, or gaseous, are usually
larger than the non-metallic inclusions, so that the
particles are accelerated more slowly and/or rise
faster under the action of buoyancy than the
inclusions. Thus, both can approach each other and
coagulate or even coalesce if they are both in the
liquid state.
The process of trapping and assimilating inclusions
by solid or liquid particles or gaseous phase depends,
among other things, on surface and interfacial
tension and the liquid metal/inclusion contact angle.
For solid and liquid particles, which might be other
solid inclusions or top slag or disper~ed slag droplets,
the wetting of a particular inclusion by liquid steel
becomes poorer with increasing contact angle, and
the force with which the particular inclusion adheres
to the other solid (or liquid) particle becomes
stronger. For contact angles greater than 90°, the
inclusion clings to any free surface of the solid (or
liquid) particle, once contact is made. The contact is
International Materials Reviews 1988 Vol. 33 No.2
strengthened by sintering. For a liqUId slag surface,
the inclusion just dilutes itself into it.
, The force of adhesion is zero for a contact angle of I
90° and it increases with the cosine of the contact
angle. Therefore, for contact angles of 110°, 121 0,
134°, or 150°, the force of adhesion is about twice,
three, four, or five times that for a contact angle of
100°. With a contact angle of 140° for alumina, the
force of adhesion is about twice that for silica with a
contact angle of 115°. Therefore clustering is more
pro bable for alumina than for silica.
The promotion of easy sticking of alumina
inclusions to other solid surfaces works not only for
the formation of alumina clusters but also when
alumina inclusions meet the inner wall of a teeming
nozzle, which then acts as a filter for the passing
stream. Consequently the build-up of alumina can be
rapid if there are many alumina inclusions in the
steel.
If the receiving phase is a liquid slag, then, with
increasing liquid metal/inclusion wetting angle, a
solid inclusion is more deeply immersed in the slag
and less deeply immersed in the liquid steel. Through
this' mechanism, it is less likely that local shear
stresses, caused by local turbulence, will tear the
particle from the interface and push it back into the
steel.
High interfacial tension between liquid metal and
non-metallic inclusion and low interfacial tension
between inclusion and receiving slag promote
inclusion coagulation with a top slag. High inter-
facial tension between liquid metal and non-metallic
inclusion, high liquid metal/gas interfacial tension,
and low inclusion/gas interfacial tension promote
adherence of the inclusion to a gas bubble.
The results of IRSID64,113 on interfacial tension
measurements show that, for sulphur or oxygen
activities in liquid steel smaller than 200 or 100 ppm,
the liquid metal/slag interfacial tension and liquid
metal/gas surface tension remain greater than
1 N m - 1 and are of the same order of magnitude.
According to Turkdogan,114 the interfacial tension
between gas and molten binary silicates, optical
glasses, alkaline earth alumina silicates, CaO-Si02-
CaF2, and FeO-MnO or CaO-Si02 or CaO-MgO-
Si02 slags remains near or below 0·5 N m -1.
With these values, coalescence between inclusions
and other slag particles or top slag, and adhesion of
inclusions to gas bubbles, are readily possible. On
the other hand, the emulsification of top slag into the
metal needs substantial energy. All these phenomena
are enhanced as the oxygen and sulphur content in
steel decreases, since the steel/slag and steel/gas
interfacial tensions increase. This is especially true for
deep desulphurisation, where an important prerequi-
site is the deep deoxidation of steel and slag. These
phenomena are reversed for high oxygen or sulphur
levels in steel, since the steel/slag and steel/gas
interfacial tensions decrease.
A. A. Deryabin and V. A. Deryabinl15 explain the
influence of the stirring intensity on the sulphur
removal by a slag as follows. (Note that the same
reasoning can also be applied to oxygen removal.)
The S concentration in the diffusion boundary layer
in the metal decreases towards the metal/slag phase
 Lange Secondary steelmaking processes 81

for alumina and silica particles increase with specific

stirring power.57 Figure 27 shows the .influe.nce ?f
various ladle treatments on the level of InclusIons In
the cast product. The pronounce~ effect of ~njection
a of calcium based powder is due In part to ItS much
greater stirring power in comparison with conven-
Ar-stirring /
tional argon stirring or RR and DR vacuum
(/)
...J treatments.
lLJ 8- \ 00 /
The mechanism for the flotation of inclusions by
>
lLJ Vacuum 0 0/ gas bubbles has been explained above. As ~oon as
...J
treatment~ bubbles and inclusions have a chance to collIde, the
Z
o 4 Powder r / / inclusion adheres to the bubble because of favourable
Vi injection \~ _ / ~
::> \ // Ll 6,
surface forces. The bubble then carries the inclusion
...J , :~ .•••A ~ upwards, driven by the remaining effective buoyancy
U A_ -
Z o force. The bubble volume therefore may compensate
2 3 4 5 6 7 for unfavourable density differences.
TOTAL OXYGEN CONTENT IN LADLE) 10-30/0 Where the oxygen potential of the system is not
under complete control, the flotation of non-m.et~llic
27 Example of influence of various ladle treat-
inclusions must be carried out by gentle stIffIng.
ments on oxygen content and inclusion levels
in cast slabs of AI-Si killed steel (Ref. 13)
With too high a stirring energy, there is an ~ncrease
in total oxygen after an initial decrease. The Increase
is due to enhancement of reoxidation from top slag
boundary, thus creating a gradient of interfacial and the lining.
tension and a capillary force directed towards the
region having the smaller values of interfacial tension Removal of inclusions by filtration
between the metal and non-metallic inclusion (i.e. This idea is based on surface forces, the mechanism
preventing the entry of the particles). The non-
of which has been explained above. Alumina
metallic inclusion is therefore repelled from the inclusions, being non-wetted by steel melt, are
boundary layer and cannot reach the phase rejected from the melt on to the filter surface, when
boundary. With increasing sulphur removal rate, the the inclusions are in close proximity to the filter pore
gradient and therefore the capillary force increases,
surface. Once the alumina inclusion makes contact
and the chance of the inclusion reaching the phase
with the filter surface, it becomes an integral part of
boundary decreases.
the filter. .
Convection, induced by stirring, must help the
Filtration studies of steel melts are in their initial
inclusion to meet the metal/slag phase boundary. At stages. Ali et al. 117 report the following res~lts of the
the instant of contact, a capillary force arises
initial stages of filtering using 2 kg melts. Sintered or
attracting the inclusion to the concave meniscus
loose granular corundum, mullite, and magnesia
acting on the surface of the inclusion from the metal/ filter materials have been successfully used to remove
slag boundary. The conditions for the inclusion to
alumina and liquid silicate inclusions from steel
pass into the slag improve as its size decre~ses .. The melts. Since the pores of the filter are larger than the
gradient of interfacial tension decreas~s wIth tIme;
inclusion, no sieving takes place at the beginning.
therefore the inclusions can more easIly reach the
For this the diameter of the filter pores and of the
slag. If there are still inclusions in the steel, then
inclusio~s must be of approximately the same size.
there has been insufficient stirring or insufficient time
Instead, the deposition of the inclusions OCC~.lfS
for them to reach the slag.
throughout the whole depth of the filter pores OWIng
Emulsified slag droplets behave differently
to diffusion, direct interception, and surface forces.
according to their size. Large ones rise rapidly
Some 60-70% of 0·5 Jlm sized inclusions are
without a metal boundary on the leading surface, so
removed; inclusions larger than 3 Jlm are removed
that the slag meets steel of bulk concentration, and
completely. .
on contact with inclusions, they are caught instantly.
Efficiency of inclusion removal can be Improved by
Smaller droplets rise more slowly and develop a
increasing filter length, decreasing melt velocity, and
metal boundary layer. Inclusions entering this layer
ensuring absence of turbulence, to increase inclusion
are subject to repulsive forces, and no inclusion
entrapment by the filter surface. High total .surf~ce
removal occurs.
area of filter increases inclusion removal effiCIencIes.
During the approach of an inclusion towards
The major drawback is low teeming capacity, the
another interface, a stage is reached where only a
melt flow rate density being less than 2 tonnes of steel
thin film of liquid hinders final contact. If no
per minute per square metre cross-section of filter.
repulsive forces are present, then drainage of this film
Ichihashi et al.11S find that inclusions in silicon
is governed by liquid viscosity.64 In this case,
killed steel are not removed by alumina, zirconia,
drainage is very rapid for small inclusions (about
mullite, or fused silica filters.
5 Jlm) and slows down with increasing inclusion size.
Gas stirring is a very efficient method for the
removal of non-metallic inclusions. A bubbling REOXIDATION
treatment removes Al203 better than a DR The term 'reoxidation' refers to an increase of the
treatment. 116 The effective mass transfer coefficients oxygen content of steel after deoxidation. The oxygen

International Materials Reviews 1988 Vol. 33 NO.2

82 Lange Secondary steelmaking processes

producing this increase comes from the atmosphere, oxygen contributions from the lining or break-
the slag, the refractory lining, and sometimes from through eye are much smaller.
oxidised steel or slag from the previous heat left on The relative stabilities of oxides in pure iron can be
the wall of the ladle. Stirring the melt promotes the seen in Table 16. The lowest oxygen content is
exchange of oxygen from regions of high oxygen obtained by the dissolution of magnesia in pure iron
potential (atmosphere, slag, lining) to regions of low for the oxides considered in this table. In steel melts,
oxygen potential (deoxidised steel). the following oxygen activities are quoted:121
Reoxidation produces new inclusions, decreases
the content of those elements in steel with a high ao = 2-6 ppm with dolomite lined ladles
affinity towards oxygen such as Al or Ca, increases Q o = 2-6 ppm with bauxite lined ladles
the tendency to nozzle blocking, worsens desul- Q o = 10-20 ppm with silica lined ladles
phurisation, and increases the apparent viscosity of Manganese and/or aluminium in steel flux silica
liquid steel. Therefore exclusion of the atmosphere, linings and/or silica shrouding tubes according to the
slag that is rich in iron oxide, and refractory lining following reactions:
with a high oxygen potential (such as an acid lining)
from contact with steel is necessary. Si02 + 2Mn = 2(MnO) + Si or
In the breakthrough zone where the bubbles of the 3Si02 + 4AI = 2(AI203) + 3Si . . (31)
gas stirring emerge, the steel is not protected by slag Si02 = Si+2Q or
and directly contacts the air, causing immediate and 3Si02 = 3Si + 6Q . (32)
direct oxidation. This problem is tackled in the
2Q + 2Mn = 2(MnO) or
'composition adjustment process by sealed argon
bubbling', by the use of a refractory lined cylinder
6Q + 4AI = 2(AI203). . (33)
lowered into the steel just outside the breakthrough It is important to consider where these reactions are
eye and filled with argon in order to decrease the likely to occur: for example, at the lining, close to the
oxygen and nitrogen potential of the atmosphere lining, or within the bulk of the melt. If, in the first
above the slag. The resulting partial pressure of case, the reaction product is solid and adheres to the
oxygen above the melt should be checked by emf lining, it can form a protective layer which slows
measurements. The same objective is pursued with a down further reaction, in which case the influence of
ladle cover on top of a gas stirred ladle. The lining dissolution on steel cleanness is at a minimum.
immersed cylinder and the cover also decrease heat Examples are the formation of Al203 or high melting
losses and serve as protection against splashing. point spinels for silica or basic linings with
In the ladle, slags of high oxygen potential cause aluminium killed steels. If the reaction product is
reoxidation of the steel and its alloying elements (e.g. liquid, the liquid forms a slag layer between steel and
aluminium). The reoxidation, however, only starts to refractory. At a critical size of this layer, it begins to
become important in practice if there is stirring in move downwards, forms ripples, and detaches as
both phases. The stirring promotes mass transfer, in droplets.
this case oxygen from slag into the metal, which is Figure 28 shows where the highest oxygen
enhanced if the top slag is dispersed into the steel. potential, due to the dissolution of a silica lining, is
This applies particularly when a strong deoxidiser, to be expected. This is diminished or strongly
such as AI, in contact with a highly oxidised slag, reduced by flotation and/or reaction with injected
causes a high flux of oxygen across the phase powder in the bubble plume.
boundary. The resulting decrease in interfacial In steels deoxidised with silicon, the composition
tension makes emulsification easier. of the liquid hot face of the lining is close to what can
The level of iron and manganese oxides in the top be expected in equilibrium with the solid phases
slag has to be less than 1% for an oxygen content of shown in Fig. 29. The liquid phase of fireclay with
the steel of around 20 ppm. Oxygen transfer from the 42% Al203 is initially in equilibrium with mullite
atmosphere across the top slag decreases with (line a-b). Al203 bricks with 85% Al203 have a
decreasing content of iron and manganese oxides. In liquid phase initially in equilibrium with alumina
both a (silica lined) ladlel19 and an RH vessel,120 it (line b-c) and flux much more slowly.
has been found that the oxidation of aluminium is During continuous casting, the success of second-
caused completely and that of carbon caused to a ary steelmaking with respect to steel cleanness may
large extent by oxygen from (oxidising) top slag. The be offset by the great danger of reoxidation. It is

Table 16 Stoichiometric dissolution of oxides in pure

iron melts (Ref. 16)

Mass action law constant at

Oxide 1900 K Contents in elements, ppm

Si02 [Si] _[0]2 = 2·5 x 10-5 267 [Si], 306 [0]

AI203 [AI]2 _[0]3 = 2·4 x 10-14 20 [AI], 18 [0]
MgO [Mg] _[0] = 1·8 X 10-6 16 [Mg], 11 [0]
MgO. Cr20; [Mg] _[Cr]2 _[0]4 = 2-4 x 10-12 82 [Mg], 356 [Cr], 219 [0]
2MgO. Si02 [Mg]2. [Si] . [0]4 = 2-0 x 10-18 27 [Mg], 16 [Si], 36 [0]
MgO .A1203 [Mg] . [AI]2 _[0]4 == 5,6 x 10-21 6 [Mg], 13 [AI], 15 [0]

International Materials Reviews 1988 Vol. 33 NO.2


Oxygen activity
c:J lowest value
~ steady state value
~ intermittent value
~ highest value
(a) (b)
a gas-bubbled ladle; b powder injection
28 Schematic model of oxygen activity distri-
bution in acid ladle (Ref. 122)
important to prevent this by using stable refractories
and by shrouding the steel streams. The partial
vacuum developed in an immersion nozzle and slide
gate valve can, however, be the cause of infiltration
of air when there is a leak in the system. The vacuum
encountered can be calculated. 123 The vacuum in the
immersed nozzle cannot be removed by injection of
purge gas: even at large gas injection rates, the most
efficient methods for the removal of a vacuum are a
maximum possible cross-section reduction at the
orifice of the immersion nozzle and a reduction of the
length of the slide gate valve and immersion
nozzle. 123
The direct cause of air entrainment by open stream
casting is the disturbance of the surface of the casting
stream. Disturbances are caused by the turbulence of
the pouring jet which is formed in the nozzle, the
intensity of which is governed primarily by the
geometry of the nozzle. The widely adopted
assumption that air entrainment by a falling jet is
only a function of its dimension, velocity, and
material properties has to be extended in order also
to consider the influence of the nozzle.
Both the experimental results and the theoretical
considerations agree that, if casting under controlled
atmosphere is not possible, it would be expedient for
industrial operation to use nozzles with rounded-off
entry shapes, ensuring good flow conditions,
minimum possible aspect ratios, and low roughness.
Moreover, low casting speeds, low casting heights,
and large stream diameters assist in the prevention of
air entrainment.124
The final (total) oxygen content in steel is a
function of the net rates of deoxidation and
reoxidation. Under plant conditions, different
reoxidation sources often limit final steel cleanness.
Lange Secondary steelmaking processes 83
29 M nO-AI203-Si02 system at 1500°C (Ref. 109)
DEGASSING
According to Sieverts law, the amount of hydrogen
and nitrogen dissolved in the metal is proportional to
the square root of the partial pressure of the
respective gas. Dissolved hydrogen or nitrogen are
eliminated from liquid steel by diffusion, by
nucleation and growth of gas bubbles, and by
scavenging with another gas. In practice, nucleation
does not play any significant role in steel degassing.
The mechanism of gas sca venging exploits the
dependence of gas solubility on partial pressure. Gas
bubbles scavenge other gases, because, within the gas
bubble, the partial pressures of the other gases are
zero. Thus, partial-pressure gradients develop,
driving the gases from the melt (and/or slag) into the
gas bubble. At the same time, this diffusion of the
other gases into the gas decreases the partial pressure
of the bubble gas. The scavenging gas is not usually
saturated with respect to the gases to be scavenged.
The amount of scavenging gas needed to attain a
certain degree of removal is greatly decreased by
decreasing the external pressure. At atmospheric
pressure, several Nm3 of scavenging gas, either
injected or produced by reaction (e.g. ~ + oxygen =
{CO }), per tonne of steel are needed for sensible
nitrogen removal. 54,125 With respect to diffusion
and scavenging, large interfacial areas, small diffu-
sion lengths, large concentration differences, and
large mass transfer coefficients are beneficial. Also
very effective is a decrease in the gas partial
pressure. 54
The pressure dependence of the desorption
reactions of hydrogen, nitrogen, and carbon
monoxide are exploited in closed vessels, which can
be evacuated, such as RR or DR degassing units.
With, for example, CO removal, it is possible to stop
a top blown heat at a higher carbon level and to use
the oxygen content of steel (and slag) to remove ~
and Q under vacuum (Fig. 30). With this method,
there is no need to squeeze the utmost out of the
BOF to produce very low carbon levels at the
expense of high oxygen and iron levels of the slag.
The advantage of combined blowing will be to use
International Materials Reviews 1988 Vol. 33 NO.2
84 Lange Secondary steelmaking processes

0·12
Q
~BOF
W
~ 0·10 ~BOF-RHor
tJ) BOF-DH
«~
wo
~ WO·OS
•...
m
zO
wo::
0')
~ a. 0.06 c BOF end point
OZ
U~
g'm
:;;cu
cuO')
~ ~ 0·04 UCIJ
(!)O 'xo U0') ~ ~e /' (RH-OB)
~>-
Om 0.02
-8.~ ~~ ~1>~~'" AI deoxidation
;(.g ttS in RH or DH
w RH or DH degassing
w
0:: (Pco=0·2atm)
lJ..
o 0·02 0·04 0·06 0·08 0·10 0·12 0·14
CARBON CONTENT)o~
30 Use of degasser for control of C and 0 levels
in AI-killed steel: Peo is partial pressure of CO
(Ref. 13)

the scavenging action of the stirring gas to promote

via the CO reaction the removal of ~ and Q without
application of vacuum. If ~ removal is required in a
vacuum degassing unit, this should be done by the
combined blowing in such a way that enough oxygen
is available for ~ removal. If not, additional oxygen
has to be supplied to the degassing unit, as has been
tried with blowing oxygen on top of the steel, or, as
is now being tried, by injecting oxygen via side wall
tuyeres into the steel in an RH vessel.
In the absence of surface active elements, the rate
determining step for hydrogen and nitrogen removal
is the phase boundary layer in the metal, or, in the
presence of a slag, the slag layer itself. An increase in
the slag layer thickness decreases the transfer rate.
In iron of high purity with very low sulphur and
oxygen content, the kinetics of nitrogen and
hydrogen removal follow a first order reaction
law.126 There is in this case,126 even for nitrogen, no
difference between desorption or absorption, as is
sometimes reported in the literature. The mass
transfer coefficient of hydrogen is at least twice that
of nitrogen.126 Temperature dependence is small.
The diffusion coefficient of hydrogen is about one
order of magnitude greater than that of nitrogen.
Surface active elements, such as Q, S, Se, and Te,
dissolved in steel reduce the transfer rate of
nitrogen. 52 Increasing the sulphur content up to
500 ppm decreases the absorption rate of nitrogen .by
about five times,127 with the mechanism of nitrogen
absorption changing with sulphur concentration. At
around 300 ppm S the rate becomes second order.127
Slag, while not capable of absorbing dry hydrogen
completely, can take up water vapour. 'The hydrogen
solubility is then proportional to the square root of
the partial pressure of the water vapour, and
hydrogen solubility is found to increase with the
basicity of the slag and with the partial pressure of
oxygen in the gas atmosphere. Unfortunately, the
largest solubilities of water vapour in CaO-AI2p3-
Si02 slags are found in those lime saturated slags,
which should be used for optimum desulphurisation,
as can be readily detected by comparing Fig. 31 with
Fig. 22.
Nitrogen dissolves in CaO-AI203-based slags
according to
(N) = Kp£j2P023/4 • (34)
its solubility increasing with decreasing oxygen
partial pressure. Under oxidising conditions, there is
practically no solubility of nitrogen in alumino silicate
slags.
Water vapour and nitrogen having dissolved in
slag, enter the metal increasing its tI, ~, and Q
levels. Emulsification of slag in metal aggravates the
problem as does direct reaction of the atmosphere
with steel at those places where th~ slag does not
completely cover the metal bath.
The net concentration of hydrogen and nitrogen in
steel is the dynamic result of pick-up and removal.
Sources for both gases are slag, moisture in solid
additions, fluxes, especially in lime, impurities and
moisture in injected gases, such as top and bottom
oxygen, stirring gas, shrouding gas, air leakage,
scrap, hot metal, injected solid materials, such as
ferroalloys, tapping, and teeming with unprotected
steel streams. While injection of liquid steel with gas
can remove hydrogen and nitrogen by the scavenging
action of the gas, it can also increase hydrogen and
nitrogen levels by pick-up from the atmosphere (gas
purity, breakthrough eye). The injection of nitrogen
gas for stirring or carrier gas purposes increases the
nitrogen content of the steel melt, while the use of
hydrocarbons for nozzle protection during bottom
injection of oxygen increases the hydrogen content of
the steel melt. A deoxidised and desulphurised steel is
prone to easy nitrification.
Hydrogen and nitrogen levels in hot metal are
decreased in BOF in the initial part of the blow. CO
bubbles produced during decarburisation scavenge
hydrogen and nitrogen, since, within the CO bubble,
the partial pressures of hydrogen and nitrogen would
be zero. Thus, partial-pressure gradients develop,
driving the gases from the melt (and/or slag) into the
CO bubble. This diffusion of hydrogen and nitrogen
into the CO bubble decreases the CO partial

International Materials Reviews 1988 Vol. 33 'No.2


pressure there, and therefore enhances decar-
burisation.54
Early additions of lime and scrap are beneficial
during steelmaking, since the scavenging action of
decarburisation can be used. Late dissolution of lime
and scrap liberates hydrogen and nitrogen at a time
of decreased CO production. Towards the end of
BOF blowing hydrogen and nitrogen levels increase
because of the reduction in the quantity of offgas
and an increase in PH20 and PN2 of the gas
atmosphere in BOF. Decisive influences on hydrogen
and nitrogen levels in this part of the blow is the
hydrogen and nitrogen entering with the lime and
scrap and with the oxygen jet (depending on the
purity of the oxygen), together with the entrainment
and/or leakage of moist air.
Appreciable additional nitrogen pick-up occurs
when CaSi is injected without a covering top
slag, 128,129 although the usual nitrogen pick-up
during the injection of CaSi or CaC2 can be halved
by additions of calcium aluminate powder.130
A casting stream of steel must be protected against
air in order to avoid pick-up of hydrogen, oxygen,
and nitrogen, with complete air tightness being
necessary, but difficult to achieve.123 Decreasing the
partial pressure of oxygen, nitrogen, water vapour,
and hydrogen by casting in an inert atmosphere is
therefore desirable.
Tapping operations of steel should be made before
deoxidation: nitrogen absorption during tapping can
then be minimised because the oxygen levels in the
undeoxidised steel impede nitrogen pick-up from the
surrounding atmosphere. Because of the partition
ratios for both gases between metal and slag, any
treatment for the removal of the gases from the steel
melt also influences the hydrogen and nitrogen
content in the slag.
Degassing steel under a slag cover also means
degassing the slag. If the slag comes into contact with
air, then only the transfer resistance of the slag
against the transfer of nitrogen and hydrogen or
moisture protects the steel from renewed nitrogen
and hydrogen pick-up. The 'degasification' of such a
slag via the steel decreases overall efficiency of steel
degassing and helps to increase the gas content of the
steel after degassing.
Oxidising slags enhance hydrogen pick-up,
whereas slags with low oxygen potential promote
nitrogen pick-up. Therefore refining slags rich in iron
oxides should impede nitrogen pick-up, and desul-
phurising slags hydrogen pick-up. But, in the latter
case, the hygroscopic nature of lime promotes
hydrogen absorption.
REACTORS FOR SECONDARY
STEELMAKING OPERATIONS
LADLE
The ladle has been transformed from a simple, cheap,
silica lined teeming vessel with a stopper rod to a
sophisticated reactor (see Fig. 1) with basic lining,
sliding gate valve, and injection devices inserted from
various directions and for, various purposes. It is
equipped with a cover which allows secure airtight-
ness and at least some decrease of the partial
Lange Secondary steelmaking processes 85
pressures of oxygen and nitrogen in the atmosphere
above the bath, and possibly with facilities for
providing heat or applying a vacuum.
RH AND DH PROCESSES
Common features
The removal of gases, especially hydrogen and CO,
constitutes an important function of both processes.
However, they are used not only to dehydrogenise
and to reduce non-metallic inclusions in steel but
also to perform decarburising and alloying under
vacuum and to control the composition and the
temperature of the molten steel.
In both processes (see Fig. 2), 5-10% of the steel
melt 'is treated in the vacuum vessel, which has a
basic lining. The atmospheric pressure outside the
vessel forces the liquid steel up to a maximum height
of 1·4 m.
Interfacial areas are greatly increased by disrup-
tion and motion of liquid steel in the vacuum vessel,
injected gas, and gas formed by reactions, such as
CO, or by scavenging, such as H2 and N2•
In the vessel, there is usually an electric resistance
heating system to reduce temperature losses, this
heating being insufficient to raise the temperature of
the steel. Additional oxygen is therefore injected into
an RH vessel through the inner tube of a double
walled nozzle which is embedded in the lower end of
the vacuum vessel in order to oxidise C (Ref. 131) or
Al (Ref. 3) and to provide the necessary heat. The
coolant gases, N 2 or Ar, are supplied to the outer
annulus, being injected into the steel in the RH vessel
and not on to it.132
Both processes can suffer from the same problem
as tank degassing, where gas removal is slow and
inefficient if there is little or no stirring of the melt.
Those parts of a stee~ bath not within the immediate
influence of the vacuum are unaffected because of the
rapid decay of low pressure with increasing ferro-
static head. The limited reduction in nitrogen levels
(in deoxidised and desulphurised steel, where the
nitrogen removal rate should be the highest)
indicates stirring deficiencies.
According to the figures given above, the bubbling
treatment in a ladle provides more stirring energy
than in either the RH or the DH process. To increase
stirring energies in the RH or D H process, the time
liquid steel needs to drain from the RH or DH vessel
has to be shortened, since the maximum tapping
height is given by the barometric head. Accordingly
recent attempts to speed up metal motion in the
vessel by increasing snorkel diameter, flowrate of gas
injected, and height of melt in vessel, and, for DH, to
increase speed of relative vertical movements of
either DH vessel or ladle, are readily understandable.
The mixing capacity of the vacuum vessel/ladle
system seems to be large enough as far as
homogenisation is concerned: more than 95%
complete mixing is obtained in RH after 0·4
circula ti ons.
The flow pattern in both processes differs from
that in gas-stirred ladles. With bubbling, the surface
of the bath is strongly agitated, while the bath near
the bottom is only weakly stirred. With the RH and
International Materials Reviews 1988 Vol. 33 No.2
86 Lange Secondary steelmaking processes
DN processes, the stirring energy is strongest at the
bottom, weakest near the bath surface, 7 5 and
relatively weak in regions in the lower part of the
ladle.133
The usual 50-75% hydrogen reduction with single
gas injection might cause difficulties in reaching
hydrogen levels below 2 ppm if initial hydrogen
contents exceed 5 ppm in ladle desulphurised steels.
No successful technique has so far been developed to
control sulphur levels in either vessel, principally
because of rapid failure of vessel refractories under
vacuum. Nevertheless sulphur control is attempted
using CaO-CaF 2-based premelted slags.3, 134
Principle of RH process
Steel is sucked into the evacuated vacuum vessel via
twin snorkel tubes, an upward motion of the steel
being produced by injection of gas into one of the
tubes. The liquid steel passes through the vacuum
vessel, leaves it by the second tube, mixes with the
remaining steel in the ladle, and establishes steady
recirculation between ladle and vessel. Double
injection of lift gas through two nozzles some
distance apart from each other increases the
circulating flowrate of molten steel and the removal
rate of carbon and hydrogen.135
The recirculation rate of molten steel (t min - 1)
increases with metal height in the vacuum chamber,
with argon flowrate up to a limiting value, and with
an increase in the inner diameter of the up tube. The
increase is proportional to the power of l·g of the
inner diameter and of 0·1 of the flowrate. It is
therefore better to increase the diameter of the,
snorkels than to increase the argon flowrate, which
does, however, have a pronounced effect on
increasing the volumetric mass transfer coefficient ka•
The combined increase of recirculation rate and mass
transfer coefficient improves decarburisation,132
giving 15 ppm rafter 20 min treatment time.
Vacuum pump capacity affects decarburisation:
with a low capacity, the beneficial effect of argon
flowrate on decarburisation is small. At a low argon
flowrate, there is hardly any influence of pump
capacity.134
Principle of DH process
By lowering the vacuum vessel (or lifting the ladle),
liquid steel enters through the degasser leg into the
tall vacuum chamber at its widest diameter.
Degassing occurs during the residence time of the
steel in the vacuum vessel. (It is to be expected that,
without any auxiliary bath motion, there will be a
rapid decay of the action of the vacuum into the
depth of the liquid.) By lifting the vacuum vessel (or
lowering the ladle), the liquid steel flows back into
the ladle, without breaking the vacuum. Repeating
the motion of vessel and ladle relative to each other
brings fresh liquid steel into the vacuum vessel. By
accelerating the speed of the vertical relative
movemen ts of vessel and ladle, and by injection of
additional gas into the degasser leg of the vacuum
vessel, degassing is greatly improved. Thus, the
recirculation rate becomes greater for a given degree
of hydrogen reduction or carbon removal. From this,
International Materials Reviews 1988 Vol. 33 NO.2
shorter degassing times result, giving savings in
refractories, energy, and time.
The vacuum chamber should be as close as
possible to the steel surface, thus allowing more steel
to flow into the chamber despite the restricted rising
height of 1·4 m. Therefore the vacuum chamber
should fit into the ladle.
LADLE FURNACE
Temperature aspects
A disadvantage of the usual secondary steelmaking
operations is the continuous decrease of the
temperature of the steel during the entire operation.
Heat losses occur by physical losses to the
surroundings and by the heating and melting of
additions, as well as by conduction through the ladle
lining and by radiation, especially from the top
surface. Conductive losses depend upon the previous
heat content of the lining, its design, material
composition, and thickness. The highest thermal
conductivity is given by dolomite, followed by high
grade alumina and fire brick, with silica the lowest.
Thus, the chemically most suited refractory material
is the least suited from a heat loss point of view.
Proper insulation is needed. Radiation losses are
minimised with a ladle cover, which should have a
larger diameter than the ladle, allowing it to be
placed like a hood over the ladle. In daily practice,
the ladle edges cannot be kept sufficiently clean to
permit the use of a simple cover that will sit tightly
enough on the rim of the ladle.
Temperature losses can be compensated for by
several means:
(i) by overheating in the melting furnace or BOF
(ii) by ladle heating using induction or electric arc
heating in air
(iii) by ladle heating using electric arc or plasma
heating in vacuum.
The first of these methods is costly, results in
remarkably increased refractory consumption and
worsened dephosphorisation, and provides only
limited heat supply. In addition, heat losses are
higher, since the temperature gradients are higher,
with more heat required for a high degree of
superheat, as compared with a similar heat treated at
lower temperatures in BOF and LF. Superheating
also requires additional furnace time.
Methods (ii) and (iii) are costly, but provide heat
and therefore relieve constraints on top slag
composition and treatment time, which are especially
severe for small ladles, and offer scheduling relief by
allowing a heat to be held in the liquid state
'indefinitely'. Since superheating is no longer neces-
sary, the general temperature level is lowered, with
its beneficial effect on overall refractory consumption
in BOF and ladle and on dephosphorisation.
Arc heating must be conducted at a pressure
greater than 40 kPa to avoid glow discharge. To
raise 1 t of liquid steel through 1 K 'requires O·5 kWh
(Ref. 136).
Ladle furnace operation
In a ladle furnace (see Figs. 1 and 2), the molten steel
is heated by submerged electric arcs and stirred by

argon at atmospheric pressure, while a high basicity
slag is formed in an atmosphere of low oxygen
potential within the ladle. It can best be described as
a very low powered EAF, in which the ladle takes the
place of the furnace shell. (Indeed a laid off small
EAF can be readily converted into a ladle furnace.)
A ladle furnace allows a basic white slag to be
produced which covers all functions pertaining to the
reduction period in an EAF, such as deoxidation,
desulphurisation, inclusion removal, reduction of
metal oxides in slag, and alloy addition. Oxidation
refining can therefore be confined to the primary
furnace (such as BOF or EAF), while reduction
refining is carried out in the ladle furnace necessita-
ting thorough separation of oxidising slag.
A ladle furnace can be provided with a tight fitting
cover with refractory lining, in order to decrease as
far as possible the partial pressure of oxygen (and
nitrogen) in the atmosphere above the slag.
Arc heating is usually carried out in the form of a
slag submerged arc, providing some protection for
the refractory lining, since part of the radiation of the
arc is absorbed by the slag. The submerged graphite
electrodes help to promote slag reduction and the
heat generated by the arc in the slag helps to
promote the formation of a liquid slag of high
basicity and fluidity. With respect to providing a
reactive slag, this form of heat supply to the steel
bath should be considered as a big advantage;
however, with respect to heat transfer to the metal, it
is inferior to a method by which the heat is generated
within the steel bath itself.
The power rating of ladle furnaces varies between
150 and 330 kVA transformer capacity per tonne of
steel to be treated. 12, 108, 137 This is 12-25 times
more heating power than is installed, for example, in
a DH vessel.138 With a ladle furnace, the total
oxygen content of molten steel is reduced to 20 ppm
or lower and the sulphur content to 20 ppm.135 The
ladle furnace increases installation cost, but total
running costs (in electric' arc steelmaking) are
reduced.139
Limitations of a ladle furnace
The limitations of a ladle furnace are as follows. The
use of lime will bring hydrogen into the steel, and,
therefore, the removal of hydrogen will not be
possible with reasonable quantities of scavenging gas,
unless a vacuum is provided. During arc heating,
there will be carbon pick-up. The treatment times are
long, the heating efficiency is low, and there are
problems due to the interaction between the arcs and
the formation of hot spots in the refractory lining,
with the radiation produced by the arcs at a
maximum at the slag line enhancing the attack of the
hot slag. The lining must be adapted to deal with this
problem, for example, by the use of MgO-C bricks
in the slag line, making use of their high resistance to
spalling and wear.
The cover on top of the ladle will not be very
efficient in decreasing the partial pressure of oxygen
and nitrogen. Only a sealed, airtight cover can be
expected to allow either real control of the
atmosphere or even the application of vacuum.
Lange Secondary steelmaking processes 87
VH D reactors
If a vacuum is applied, one arrives at the principle of
VHD (vacuum heating degassing). More commonly
used is the abbreviation VAD (vacuum arc
degassing); this does not include plasma heating.
Two systems use this principle: Finkl- Mohr and
ASEA-SKF.
In the Finkl-Mohr process (see Fig. 2), the ladle is
placed inside another reaction vessel, which can be
evacuated. The ladle content is stirred by bubbling
argon through a porous plug, and heat is supplied
by electrodes introduced through vacuum tight
mountings. The process is characterised by the arc
heating of molten steel under reduced pressure.
The ASEA-SKF process (see Fig. 2) uses two
operating stations. The vessel is placed under one lid
for electric arc heating and then transferred under the
second lid for vacuum degassing. Stirring is by'
induction coils located on the ladle transfer car and
by additional gas stirring. Application of vacuum or
heating is carried out under separate roofs, and the
sequence of operations is optional. Lime-fluorspar
based desulphurisation powders are added in the
heating station; alloying materials can be added at
both stations. For deep desulphurisation, additional
desulphurisers, such as CaC2, CaSi, AICa" and misch
metal, should be added. The two station operation
results in an increase in hydrogen after degassing,
especially if a treatment with calcium bearing
materials follows the degassing operation.
As discussed above, induction stirring is less
efficient than gas stirring, especially with respect to
hydrogen removal in fully killed steel, where there is
not the additional scavenging action of CO. 54 Owing
to the poor mixing at the slag/metal interface by
induction stirring coupled with the need to decrease
as far as possible lining wear, total processing time
may extend up to several hours. The use of a non-
ferromagnetic ladle shell, either an austenitic stainless
steel or some composite plastic material, is
mandatory.
For an ASEA-SKF treatment, the operational
cost is 7'5 times that for argon stirring and 5·4 times
that for RH treatment. 42 In another comparison, it
has been found that the treatment of liquid steel low
in hydrogen, nitrogen, and carbon in an ASEA-SKF
+ vacuum reactor is about twice as expensive as in a
TN reactor.140
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International Materials Reviews 1988 Vol. 33 No.2