Kinetics of Fundamental Reactions
Steelmaking Process*
By Kaxumi MORI **
Synopsis
This is a review of kinetic studies on fundamental reactionspertinent to
steelmakingprocesses. With citing research results mainly obtained in the
author's laboratory, description of the paper is made aiming at showing
the present state of the knowledge on the selected subjects. Results of
studies on the behavior of bubblesand jets at the submergedorifice(nozzle)
are reviewed. The mixing characteristics in a gas-stirred molten metal is
discussed. Kinetic studies on carbon-oxygenreactions and nitrogen reac-
tions in molten iron are presented. Comments are made on the rate-con-
trolling mechanism of slag-metal reactions. A summary is made of the
results of studies on the rate of mass transfer between molten slag and
metal influencedby gas injection. Kinetic problems in scrap melting and
the rates of dissolutions of solid iron and Cr203 in liquid iron withforma-
tion of CO are handled.
Key words: steelmaking ;reaction kinetics; injection metallurgy; bubbl-
ing; jetting; nozzle clogging; gas-metal reaction; slag-metal reaction;
scrap melting; reduction of Cr203.
I. Introduction
To understand scientifically the phenomena oc-
curring in steelmaking processes, it is required to in-
tegrate the knowledge from the two basic aspects, that
is, thermodynamic equilibrium and kinetics. Look-
ing back to the state of research in the field of the
physical chemistry of steelmaking processes in the six-
ties, one finds that compared with a wealthy stock of
knowledge on thermodynamic properties of materials
and equilibrium of fundamental reactions, studies
from the aspects of kinetics and process science had
been awfully poor. This situation was clearly de-
scribed by F. D. Richardsoni~ in the 1964 Howe Me-
morial Lecture of the Iron and Steel Division of
AIME.
The reactions in steelmaking processes are complex
in that they occur in heterogeneous phases. The
rates of the reactions are largely controlled by heat
and mass transfers which are in turn influenced by
momentum flow. Hence, the kinetic studies on steel-
making reactions require the tools of thought devel-
oped in the field of chemical engineering.
From the pioneering work of L. S. Darken,2~ C.
Wagner,3> and F. D. Richardson,i~ we recognized the
importance of mass transfer in steelmaking reactions.
In 1970 a unique International Conference was held
in Aachen on " Kinetics of Metallurgical Processes in
Steelmaking ", in which the state of theoretical knowl-
edge on kinetics of mass transfer in metallurgical sys-
tems was presented in a self-contained survey.4) The
John Percy Research Group in Process Metallurgy of
Imperial College held a noteworthy symposium in
1966 on " Heat and Mass Transfer in Process Metal-
* Manuscript received on September 2, 1987; accepted
**
Department of Metallurgy, Nagoya University, Furo-cho,
(246) Review
Pertinent to
lurgy ". Accumulated knowledge on kinetics of gas-
slag-metal reactions is critically compiled by Rich-
ardson in the famous textbook Physical Chemistry of
Melts in Metallurgy, II.5~ The Iron and Steel Institute
of Japan held The 7th Nishiyama Memorial Seminar
in 1966 on " Fundamentals in Iron and Steelmaking
Processes " in which Y. Kawai and the author han-
dled kinetic problems.
The present paper is a review of kinetics of selected
aspects of fundamental reactions pertinent to steel-
making processes with presenting research results
mainly obtained in the author's laboratory during the
last two decades. The subjects presented here are,
1) the behavior of bubbles and submerged gas jets
in liquid metals;
2) reactions between liquid metals and gases;
3) reactions between liquid metals and slags; and
4) dissolution of solids into liquid metals.
Throughout the presentation, rate-determining mech-
anisms and mass transfer problems are critically dis-
cussed.
II. Injection Phenomena in Liquid Metal
Techniques of submerged gas and powder injection
are playing important roles in modern steelmaking
processes. Over the years much fundamental work
has been done on the kinetics of interactions between
injected gas and/or powder and liquid metal. The
present chapter deals with selected problems in injec-
tion phenomena.
1. BubbleFormationfrom Single Nozzle in Liquid Metals
Knowledge on the size of bubbles forming at a sub-
merged orifice in liquid is indispensable in the kinetic
studies of mass transfer between injected bubbles and
liquid metal. The equations correlating the size of
bubbles can be classified in accordance with the range
of gas-flow rates.
(1) At low gas-flow rates (Region (I)), the bubble
size is independent of the gas-flow rate and is given
by the following equation.
d 6adn 1/3
B= ........................(1)
Pig
where, dB: bubble diameter (cm)
6: surface tension of liquid (dyn/cm)
do : nozzle diameter (cm)
Pi : liquid density (g/cm3)
g: acceleration of gravity (cm/s2).
(2) At higher gas-flow rates (Region (II)), the
in the final form on November 13, 1987, © 1988 ISIJ
Chikusa-ku, Nagoya 464,
 Transactions ISIJ, Vol. 28, 1988 (247)

bubble size depends only on the gas-flow rate and noz- pends on the liquid physical properties is attained.
zle diameter. The empirical correlation obtained by It is clear that at low gas-flow rates the bubble size is
Davidson and Amick by air-water and air-oil sys- determined by a force balance under the static condi-
tems6) is tion while at higher gas-flow rates a balance between
the upward acceleration of the liquid surrounding the
dB = 0.54(Vgdo.5)o.289
.....................(2)
bubble and the buoyancy force becomes important in
where, Vg; the gas-flow rate (cm3fs). determining the bubble size.
Equations (1) and (2) were obtained for bubble Sano and Mori10) determined the size of bubbles
formation from wetted nozzle in water and organic in the bubble swarms in mercury from measuring the
liquids. In this case do is equated to the inner nozzle bubble frequency by using an electroresistivity probe
diameter. The applicability of these equations to technique. From examining the effect of liquid physi-
non-wetted nozzles in various liquid metals was inves- cal properties on the size of bubbles in the swarms,
tigated in the author's laboratory.7-9> the following general equation is obtained.
The metals used were mercury, molten silver, and
molten iron. Bubbling was performed through a noz-
zle, the tip of which was of the upward faced type.
vs - 0.091
(c)O.5
0.44
s ..................(4)
The bubble volume was determined from the volu-
where, dvs : volume-surface mean diameter of bub-
metric gas-flow rate and the frequency of bubble for- bles (cm)
mation.
VS: superficial gas velocity (cm/ s).
It was found that the non-wettability of the nozzle The size of bubbles in molten iron estimated from
in liquid metals has decisive influence on the bubble
Eq. (4) is compared with that estimated by Fruehanil)
size. When the outer nozzle diameter was adopted for Q; BOP.
as do in Eqs. (1) and (2), close agreement between
the experimental results for liquid metals and calcula- 2. BubblingJetting Phenomenain Gas Injectioninto Liquid
tions was obtained. This finding has a significant
This section is concerned with the behavior of gas
meaning in practice such as gas bubbling through a
jet near the orifice. A series of studies has been made
porous plug in molten steel. in the author's laboratory on the behavior of injected
Based on the experimental results, an empirical
equation to predict the size of bubbles in a wide gas jets at a submerged orifice in liquid over a wide
range of gas-flow rates extending to the region of sonic
range of gas-flow rates is given by
velocity.l2-16) To know the influence of gas and liq-
uid properties on jet behavior, three models of ni-
dB
={()
6Q
Plgn2+0.0242(V2dn)0.867
g }1/6
.........(3) trogen-mercury, nitrogen-water and helium-water
systems have been employed. The jet behavior ex-
Equation (3) becomes Eq. (1) at low gas-flow rates, clusively in the initial jet formation zone was observed
while it agrees with Eq. (2) at higher gas-flow rates. by using a visual technique.
Sizes of bubbles formed in various liquids are cal- The formation of a bubble at a submerged orifice
culated by using Eq. (3) and compared in Fig. 1. in liquid can be represented by a rectangular wave
Here, the calculation is made for the nozzle of 0.6 the height and width of which are equal to the maxi-
cm in diameter. As seen from Fig. 1, at low gas-flow mum bubble base diameter (dM) and the bubble for-
rates the bubble size decreases in the order of de- mation time, respectively. Figure 2 is an example of
creasing a/pi, that is, molten iron, water, molten silver rectangular waves showing successive formation of
and mercury. As the gas-flow rate increases, the dif- bubbles for nitrogen injection into mercury. Here,
ference in the value of bubble size becomes smaller two phenomena are distinguished. One is the forma-
and the region where the bubble size no longer de- tion of bubbles of various base diameters. This is
called " bubbling ". Another phenomenon is that an

Fig, 1. Comparison of size of bubbles formed in various Fig. 2. Bubble base diameter (dM) vs. time at a high gas-
liquids.° flow rate.13j

Review
(248) Transactions ISIJ, Vol. 28, 1988
apparent coincidence between the base diameter (4)
and orifice diameter (do) occurs over various ranges
of time. In these time ranges the injected gas leaves
the orifice as a continuous jet of gas. This phenome-
non is called " jetting ". Figure 2 exhibits the alter-
nation of jetting period with bubbling period. The
phenomenon of bubbling observed here is considered
to be very similar to that of " back-attack " observed
by Ishibashi et a1.17)
In Fig. 3, the time fractions for both bubbling and
jetting are plotted against the gas-flow rate for nitro-
gen gas injection into mercury. As shown clearly in
the figure, jetting is initiated at a critical gas-flow rate
for each orifice diameter. With increasing gas-flow
rate jetting fraction increases and bubbling fraction
decreases. However, in the explored range of gas-
flow rates perfect jetting did not occur. Thus, it has
been cleared that a gradual change from bubbling to
jetting takes place in a transitional gas-flow range.
Similar bubbling jetting phenomena were observed
for nitrogen-water and helium-water systems.
In Fig. 4, the time fraction for bubbling jetting is
plotted against the nominal Mach number M' for gas
injection into mercury and water. Here, M' is de-
fined as the ratio of nominal gas-flow velocity to the
sonic velocity. The dotted line and broken line in
the figure indicate the subsonic-sonic boundary for
nitrogen injection and that for helium injection, re-
spectively. The values of M' at the boundary are
calculated theoretically on the basis of fluid dynam-
1cs.13)
Fig. 3. Time fractions for bubbling and jetting plotted
against gas-flow rate (N2 Hg system).13)
Fig. 4. Time fractions for bubbling and jetting for three
models plotted against nominal Mach number.1s~
As seen from Fig. 4, the critical value of M' at
which the transition from bubbling to jetting begins
to occur is very close to the subsonic-sonic boundary
almost independently of physical properties of gas and
liquid. The critical value of M' for nitrogen injection
into mercury was found to be the same for the three
orifice diameters as shown in Fig. 12 of Ref. 13).
The most important finding is that jetting occurs
in the sonic flow region. It is presumed that the gas
jet whose flow velocity is equal to the sonic velocity
at the exit of the orifice becomes a supersonic jet be-
yond the exit.14) To the best of our knowledge, these
were the first to show.
From Fig. 4, it is seen that the value of M' required
to achieve a given jetting time fraction increases with
decreasing gas to liquid density ratio. This finding
could be ascribed to the fact that the stability of the
gas jet influenced by bath movement increases with
decreasing the liquid density and with increasing the
injecting gas density.
Concerning bubbling behavior, further detailed ob-
servations were made. " No linking " time, that is,
the time interval between the severance of the first
bubble from the gas supply and the subsequent link-
age of the severed bubble to the forming second bub-
ble was measured.15) On the basis of results of this
study combined with those of the above-described ob-
servations on the bubbling jetting transition, appar-
ently different views on the gas jet characteristics
proposed by various investigatorsl$_21)could be cor-
related with each other.l5)
Physical behavior of injected gas in the initial jet
formation zone has important connections with serious
process problems such as refractory erosion due to jet
action and clogging of tuyeres by frozen metal.
Sakaguchi et al.22>made an important investigation
on the erosion of a double-tuyere for injection of oxy-
gen into molten steel. From their data giving the
injection condition under which the tuyere refractory
is little eroded, Mori et al.12"3)have estimated the criti-
cal Mach number for erosion of the tuyere refractory
used for injecting oxygen into steel bath. In Fig. 4
the value of this critical Mach number is shown by a
dot-dash line. It is seen that the estimated value
almost coincides with the critical velocity for the bub-
bling-jetting transition in the He-H20 and N2-Hg
models. Thus, it has been cleared that the bubbling-
jetting transition is of considerable significance in the
practical problem of erosion of the tuyere refractory.
Studies on the mechanism of the penetration of liq-
uid back into the tuyere during gas injection are very
few. Engh et al.,23) from model studies of gas injec-
tion in water and glycol, obtained a correlation equa-
tion for the formation velocity of droplets entering into
the nozzle. However, a criterion for predicting liquid
penetration leading to nozzle blocking was not given.
Marukawa et a1.24)found, from studies of gas injection
in a 250 t ladle, that gas injection at sonic velocity is
necessary to prevent nozzles from clogging. Very
recently, Sharma25) has done experiments of injecting
inert gases into molten steel. He concluded that the
controlling factor for metal penetration in the tuyere

is the jet Froude number, and not the gas velocity
(Mach number). According to him, injecting gases
at sonic or supersonic velocity may not be sufficient to
prevent metal penetration.
3. Penetration of Solid Particle into Liquid Metal
In the process of submerged powder injection,
whether the particle passes through the gas-liquid
interface or becomes trapped inside bubbles is one of
the most fundamental problems. Engh et al.26~dis-
cussed this problem by using a theoretical model
based on the equation of motion of a sphere moving
in liquid. However, their model has not been verified
experimentally.
Ozawa and Mori27~have made a study of the pene-
tration of a spherical body dropped onto a stagnant
mercury bath. The penetration behavior was re-
corded by a high speed cinecamera. In Fig. 5, the
critical entry velocity calculated from the critical
dropping distance by using the free fall equation is
plotted against the diameter of the spheres of various
materials. This experimental result is well explained
by the calculation using a theoretical model for the
critical condition for the penetration of the sphere into
the liquid. It is found that the virtual mass of the
sphere and the cavity formation have important mean-
ings in the mechanism of penetration of particles into
liquid.
4. Mixing Characteristicsin a Gas-stirred Molten Metal
Bath
Fluid flow phenomena and mixing characteristics
in steelmaking processes have decisive influences on
the steelmaking reaction rate. Many experimental
and theoretical studies have been made on circulating
flow and mixing time in the molten metal bath.
Nakanishi et al.28~have first introduced the concept
of mixing time to evaluate the mixing characteristics
in the steelmaking processes and obtained a quantita-
Fig . 5. Critical entry velocity for penetration
liquid plotted against sphere diameter.27~
Transactions ISIJ, Vol. 28, 1988 (249)
tive relation between the mixing time tm and the
stirring power per unit mass of melt &M.
Sano and Mori29~ noticed that the relations
between tm and ~M obtained from experiments on
different bath sizes scatter largely. They made a
theoretical analysis on circulating flow in a bath by
setting up a steady-state energy balance equation.3o)
They showed that tm is dependent not only on the
~Mbut also on sizes of the bath and the plume (bub-
ble dispersed zone). Their theoretical correlation is
shown by a solid line in Fig. 6, in which the experi-
mental results obtained using water models and 6, 60 t
ladles are also shown. The mixing time tm is in in-
verse proportion to sM(D2fHo)-2 roughly to the one-
third power. Here, D is the bath diameter, and Ho
is the bath depth. Close agreement between the
calculation and the experiments is seen in the figure.
Asai et al.31~made a dimensional analysis of mixing
time on the basis of Navier-Stokes equation and ob-
tained correlating equations corresponding to the flow
regimes. If the mixing length is equal or propor-
tional to the characteristic length of the bath, their
equations for laminar and turbulent flow regimes are
similar to the equation obtained by Sano and Mori.29~
A mention is made here of the definition for the
stirring power of injected gas specially because of dis-
agreements among investigators. Several investiga-
tors overestimated the stirring power by assuming that
the work done by a bubble during its rise is the sum
of work done by the buoyancy force and the volu-
metric work. This sum is exactly twice the actual
work done by a bubble during its rise.
III. Kinetics of Gas-Metal Reactions
Kinetics of reactions between gas and molten iron
have been studied extensively during last three dec-
ades. Characteristic features in the mechanisms of
decarburization of molten iron-carbon alloys, desorp-
tion of CO and absorption-desorption of nitrogen in
molten iron, and absorption of oxygen into molten
iron are fairly well understood. In the present chapter
three subjects in which the author has had a great
interest will be presented.
of sphere into
Fig. 6. Relation between mixing time and sM(D21Ho)-2, 30)
 (250) Transactions ISIJ, Vol. 28, 1988
1. Carbon-OxygenReactionsin Molten Iron
1. Nucleation of CO Bubbles in Iron Drops
In the experiments of decarburization of molten
iron-carbon alloys by using the levitation technique,
nucleation of CO bubbles was observed to occur in
levitated drops whose carbon concentration decreased
to lower levels and oxygen concentration began to in-
crease.32) The nucleation occurred at CO pressures
(Pco) of 10' 100 atm in equilibrium with the bulk
carbon and oxygen concentrations. The values of
Pco are much lower than 104atm calculated from the
homogeneous nucleation theory. Therefore, the mech-
anism of CO nucleation had been left uncleared.
A creative work for nucleation of CO bubbles in
iron drops was done by El Kaddah and Robertson.33)
They employed a high pressure levitation melting
technique. A drop of iron-carbon alloy was brought
to equilibrium with CO-C02 gas mixtures at high
pressures of l0-'8O atm. Then, the gas pressure was
dropped suddenly to atmospheric pressure, bringing
about supersaturation of dissolved gases in molten
iron. By observing the nucleation event using a cine-
camera, the critical supersaturation for CO bubble
nucleation was determined. The data of the super-
saturation pressure are plotted in Fig. 7 as a function
of oxygen activity in the iron-carbon alloys. As seen
from Fig. 7, the supersaturation pressure decreased
markedly from N 70 atm at Pco,/Pco N 2 X 10_2to N 10
atm at P002/P00N(6'8) X 10-2. Here, Pco2/Pco rep-
resents the oxygen activity in the iron as defined by
CO+0 = C02 ................:.......(5)
ao = (Pco2/Pco)/K .....................(6)
2. Kinetics of Interfacial Reaction of Decarburization of
Molten Iron by Carbon Dioxide
One of the most serious problems discussed on the
rather academic studies of decarburization of molten
iron has been the importance of the interfacial reac-
tion kinetics in controlling the overall reaction rate of
decarburization. Nomura and Mori34)made a kinetic
study of decarburization by blowing CO-C02 gas
mixtures onto the inductively-stirred iron-carbon
melts. At " high " carbon contents, the apparent
Fig . 7. Supersaturation limits for nucleation of CO
in Fe-C---O at 1600°C.33)
-
rate of decarburization is independent of carbon con-
centration and markedly influenced by the flow rate
of CO-C02 gas mixtures. A reaction model involv-
ing both the gas-phase mass transfer and the chemical
process of C02 dissociation on the melt surface is de-
veloped. Here, the rate of chemical process of de-
carburization (mol/cm2. s) is expressed by
J'kP002
to= ........................(
From applying the reaction model to the experimental
data, the rate constant, k, is presumed to be higher
than 0.001 mol/cm2. s. atm (Fig. 8).
Samnand Belton35)succeeded in studying kinetics of
decarburization of liquid iron in a precise regime of
interfacial reaction control. They did experiments
of decarburization by C02 with continuously carbon-
saturated iron and iron with varying carbon concen-
tration at 1 160 to 1 600°C under conditions where
mass transport of reactants is not rate controlling.
The obtained rate constant is shown in Fig. 8. Trace
amounts of sulfur were found to give a marked effect
on the rate constant. Interestingly, the rate constant
obtained by Samnand Belton35)is comparable to that
presumed by Nomura and Mori34) as its lowest limit
value and also extrapolated value of the rate con-
stant for the decarburization of solid iron.3s)
More recently, Cramb and Belton37) have studied
the rate of dissociation of C02 on liquid iron by means
of the 14002-CO isotope exchange reaction. They
show that the value of the rate constant for the dis-
sociation of C02 for pure liquid iron surface at low
oxygen potential is consistent with that for the de-
carburization of liquid iron by C02.
3. Rate of Desorption of CO from Liquid Iron and Iron
Alloys
Suzuki and Mori38) made experimental studies on
the rate of CO desorption from liquid iron by flushing
Ar over the melt. In Fig. 9 the apparent mass trans-
fer coefficients of carbon and oxygen are plotted
against the ratio of the concentrations of carbon and
oxygen. The rate of CO desorption from the melt is
controlled by mass transfer of carbon or oxygen in
the melt. The composition of the melt corresponding
to the transition from carbon- to oxygen-transfer con-
b ubbles Fig. 8. Comparison of the rate constant of decarburization
between liquid and solid iron.

trol is expressed by
Go/Go = ko~kc
where, CC,C0: concentration of C and O (mol/cm3)
kc, ko: mass transfer coefficient of C and O
(cm/s).
The results are explained fairly well by the model of
liquid-side mass transfer.
The technique similar to that used in the above
work was applied by Suzuki et a1.39~to study the
effect of Co, Ni and Cr on the rate of CO removal
from liquid iron. As presented in Fig. 10, the mass
transfer coefficient of oxygen (k0) is little affected by
addition of Co or Ni, while k0 for the Fe-Cr alloy
decreases markedly with increase of Cr content. The
results could be interpreted reasonably in terms of
thermodynamic interaction parameters in the alloy
systems.
2. Kinetics of ReactionsbetweenLiquid Iron and Nitrogen
Kinetics of nitrogen absorption and desorption in
liquid iron is an attractive problem from both aca-
demic and practical points of view. In the sixties and
seventies numerous studies were made on this subject.
A review of the kinetic studies of reactions between
Fig. 9. Relation between k0, kc and Cc/C0.38)
Fig. 10. Effect of X (X: Go, Ni, Cr) on the mass transfer
coefficient of oxygen at 1580°C.3s)
Transactions ISIJ, Vol. 28, 1988 (251)
liquid iron and nitrogen is very instructive in the his-
tory of basic research for steelmaking reactions.
The rather earlier work was that done by Pehlke
and Elliott40~who measured the rate of the reaction
of nitrogen with liquid iron by using a modified
Sieverts apparatus. In this study, the rates of ab-
sorption and desorption were found to be equal and
controlled by a first order reaction. Taking also into
consideration the experimental results that the rates
were greatly influenced by inductive stirring in the
metal phase, Pehlke and Elliott40~concluded that both
the rates of absorption and desorption were controlled
by mass transfer in the melt.
In all kinetic studies made in Japan on the reac-
tions of nitrogen absorption and desorption, tech-
niques of gas blowing onto the iron melt were em-
ployed. It was shown that the absorption of nitrogen
in liquid iron of low oxygen content was controlled by
the mass transfer of nitrogen in the liquid.41~
A serious problem arose from the studies on the
desorption of nitrogen into pure argon. It was shown
first by Banya et a1.42~that the desorption of nitrogen
obeyed the second-order kinetic law. Other inves-
tigators,43,44~including Choh et al.45~who studied un-
der reduced atmosphere, all obtained the same result
on the kinetics of nitrogen desorption. The rate can
be described by the equation:
_ d[%N] _k, A [o N 2 $
where, k' : ` apparent ' reaction rate constant (cm/
%.s)
A : metal-gas interfacial area (cm2)
V: metal volume (cm3).
In Fig. 11 the data on the relation between the ap-
parent reaction rate constant and oxygen concentra-
tion in liquid iron obtained by various investigators
are compared. The value of k' clearly decreases with
increasing oxygen concentration. Thus, it has been
concluded that the desorption of nitrogen into pure
argon is controlled at least partly by the chemical
Fig. 11. Effect of oxygen on the apparent rate constant of
nitrogen desorption from liquid iron at 1600°C.4s)
(252) Transactions ISIJ, Vol. 28, 1988

reaction. This is the first result showing that not all
steel refining reactions is controlled by mass trans-
fer.
Comparison of the mechanisms of nitrogen absorp-
tion and desorption in liquid iron stated above pre-
sents the apparent discrepancy existing between the
two processes. This kind of discrepancy was called as
" asymmetry of absorption and desorption " in the
paper by King et al.46~ It appeared that this " asym-
metry " is inconsistent with the microscopic reversi-
bility of chemical reaction.
Sano et al.47~proposed a mixed control model for
the kinetics of gas-metal reactions in which the over-
all reaction rate is controlled both by surface reaction
and by mass transfer in the metal neglecting gaseous
mass transfer. This model gave a reasonable expla-
nation of the type of the rate equations. Chatterjee
and Bradshaw48~developed equations relating the over-
all mass transfer coefficient with liquid and gas phase
coefficients and gave a diagram showing the relative
importance of liquid phase mass transfer coefficient in
determining the overall coefficient. The study by
Chatterjee et al. suggested possibility of solving the
problem of " asymmetry of absorption and desorp-
tion ".
Mori49~obtained the overall rate equation for gas
absorption and desorption in liquid metal expressing
that the overall rate is controlled by the three pro-
cesses of gas and liquid phase mass transfers and in-
terfacial chemical reaction and showed a diagram
similar to that by Chatterjee and Bradshaw.48~ Re-
ferring to this diagram, one could explain very rea-
sonably the apparent discrepancy in the kinetics
between gas absorption and desorption.
It is to be noted in Fig. 11 that the data of k' ob-
tained by various investigators scatter in low oxygen
concentration range much more than those in higher
oxygen concentration range. This problem was in-
terpreted by Choh et a1.45~who pointed out that the
rate of nitrogen desorption is controlled by liquid
phase mass transfer as well as by interfacial reaction
kinetics.
which was faced upward. The immersion depth of
the nozzle was 3.3-.4.7 cm. The gas-flow rate was
70 117 Ncm3/min. The oxygen and sulfur concen-
trations in the melt were varied widely. During each
experiment the frequency of bubble formation was
measured to calculate the volume of a bubble formed
at the nozzle.
Figure 12 shows a typical example of change in
nitrogen concentration with time. The rate data ex-
pressed as the nitrogen absorption efficiency were
compared with those calculated by using a mixed
control model of liquid phase mass transfer and chem-
ical reaction at the bubble-metal interface.50~ In the
model calculation, nitrogen absorption is considered
to take place during both bubble formation at the
nozzle tip and bubble ascent. The chemical reaction
rate constant k~ is determined by the trial and error
method in comparing calculation with experiment and
presented in Fig. 13 by closed circles. It is seen that
k~ decreases with increasing [%O]+[%S]/2.
2. Rate of Nitrogen Desorption from Molten Iron by Ar
Injection51
The experimental apparatus and method used for
the study of nitrogen desorption were almost similar
to those of nitrogen absorption. The injected Ar gas-
flow rate was 74N96 Ncm3/min. During each experi-
ment, an argon-nitrogen gas mixture whose nitrogen
concentration was controlled to be in equilibrium with

3. Rate of Nitrogen Absorptionand Desorption in Liquid

Iron throughInjectedBubbleInterface
From both academic and practical points of view, Fig. 12. Change in nitrogen concentration with time.5o~
attention has been paid these years on the kinetics of
gas-liquid iron reactions through the injected bubble
interface. To make theoretical analyses of experi-
mental data of this kinetics, knowledge on the size of
injected bubbles is essential. The author and his
co-workers, on the basis of the information on the
formation of bubbles in liquid metals obtained in their
laboratory, have made a series of studies on nitrogen
reactions of liquid iron with gas injection. Below,
summarized description of these studies will be made.
1. Rate of Absorption of Injected Nitrogen Bubbles in
Molten Iron5O~
The study was made by using a Tammann furnace
to melt iron in a magnesia crucible. Nitrogen was
injected into the melt through an immersed alumina Fig. 13. Chemical reaction rate constant plotted against
nozzle of 0.1 cm I.D. and 0.3 cm O.D. the tip of [%o1 +[%S]/2.°
 Transactions ISIJ, Vol. 28, 1988 (253)

Fig, 14. Efficiency of nitrogen desorption.51)

Fig. 15, Comparison of change in nitrogen concentration
with time by Ar injection together with blowing

the nitrogen concentration in the melt was blown onto
the melt, so that the reaction through the free surface
could be neglected. From nitrogen concentration vs.
time relations, the efficiency of nitrogen desorption of
injected Ar (f) is calculated. Figure 14 shows typical
examples of the relation between f and the nondimen-
sional nitrogen concentration B (=[%N]/[%N]e),
where [%N]e is nitrogen concentration in molten iron
in equilibrium with nitrogen pressure of 1 atm. A
mixed control model is developed in which mass trans-
fers in both liquid and gas phases and chemical reac-
tion at the bubble-metal interface are considered to
be rate controlling. The chemical reaction rate con-
stant is determined from the comparison of the effi-
ciency of nitrogen desorption between model calcula-
tion and experiment and plotted in Fig. 13 by open
circles. As can be seen from Fig. 13, ke determined
from the study of nitrogen desorption agrees well with
that of nitrogen absorption. Very interestingly, ke
thus determined is in good agreement with that ob-
tained by Byrne and Belton52)from an experiment of
the isotope exchange reaction. Considering the fea-
ture of the plotting embodied in Fig. 13, one could
conclude that both nitrogen absorption and desorp-
tion in molten iron are controlled by mass transfer
and chemical reaction and that k~ obtained rather
indirectly from the comparison between experiment
and calculation is the real chemical reaction rate con-
stant.
3. Rate of Nitrogen Desorption from Molten Iron by
Argon Injection Together with Blowing onto the Melt53)
In earlier stage of the progress of the study of nitro-
gen desorption presented in the previous section,
Takahashi et a1.53)got a preliminary result shown in
Fig. 15. The open circles represent the data for ni-
trogen desorption by Ar injection together with blow-
ing onto the melt. The closed circles represent the
experimental result with Ar blowing onto the melt.43)
The dotted line shows the change of nitrogen concen-
tration calculated for the desorption through the bub-
ble interface. It is clear that the rate of nitrogen
desorption with Ar injection is enhanced markedly by
Ar blowing onto the melt. Possibly, a high degree of
turbulence is produced from the appearance of bub-
bles at the surface of the melt, leading to the increase
onto the melt.53)
Fig. 16. Ratio of the effective surface area of the melt to the
cross sectional area of the crucible.53)
of the effective free surface area (AS).
On the basis of this preliminary result, Takahashi
et al.53)made a systematic study for the enhancement
of the rate of nitrogen desorption from molten iron by
Ar injection together with blowing onto the melt. It
has been cleared from the comparison between cal-
culation and experiment that the effective free surface
area of the melt is about 2.1 times as large as the
cross sectional area of the crucible (Ae) (Fig. 16).
Furthermore, Takahashi et al.54)have observed that
the rate of nitrogen desorption using A1203 crucible
is lower than that using MgO crucible. Deoxidation
with Al also lowered the rate. In these cases, inter-
facial resistance was found to exist at the free surface
of the melt, retarding the rate of nitrogen desorption
through the free surface.
Iv. Kinetics of Slag-Metal Reactions
1. Slag-Molten Metal ReactionswithoutFormation of CO
Slag-metal reactions at high temperatures, partic-
ularly those without formation of CO, are generally
assumed to be controlled by the rates of transport of
reactants and products in the slag and metal phases.
Brimacombe and Richardson,55) in a study on the
mass transfer in the reaction of Tl(in Pb)-Pb2+ (in
fused salt), have calculated from the estimation of the
(254) Transactions ISIJ, Vol. 28, 1988

exchange currents for the separate reactions

Pb (l) = Pb2++2e .....................(9)
T1= TP +e ...........................(10)
that the chemical rates for the combined reaction are
some 60-'100 times the measured rates in the initial
stage of the reaction. Schwerdtfeger et a1.56'57) have
measured the exchange current densities for the reac-
tions
Fe (s) = Fe2+(slag)+2e at 1450°C
........................(11)
Si (Co-5%Si) = Si4+(slag)+4e at 1600°C
........................(12)
and concluded that slag--metal reactions involving iron Fig. 17. Effect of stirring on apparent mass transfer coef-

and/or silicon under industrial process conditions are ficient.5a)

very unlikely controlled by the transfer kinetics of re-

action (11) or (12).
More direct evidence for determining rate-control-
ling steps has been obtained from the study on the
kinetics of the reaction
Si (in Cu)+2FeO (in slag) = 2FeO (in Cu)
+5i02 (in slag) ....................................(13)
by Mori et a1.58~ The slag was of FeO-containing
Li2O-SiO2-A12O3system. The rate of reaction (13)
was found to be described by
o°

dt Vm
where, A : the interfacial area
Vm: the metal volume
ks1: the apparent mass transfer coefficient of
silicon.
In Fig. 17 ks1 is plotted against the rotational speed
of the stirrer, R. ks1increases just in proportional to
the square root of R (rpm). This strongly supports
the view that the reaction is of mass transport con-
trolling.
Mori et a1.,58~in the course of kinetic study of reac-
tion (13), have observed a tendency for the apparent
mass-transfer coefficient in the metal phase (ks1) to in-
crease with lowering of Si concentration in the metal.
To investigate the mechanism of this phenomenon a
series of experiments has been done by Hirasawa
et a1.,59~where initial concentration of Si ranged from
0.01 to 0.14 %. Typical results are shown in Fig.
18. It is indicated that ks1 is almost constant at
relatively higher initial Si concentration ([%Si]0),
while at lower [%Si]0, ks1increases with decreasing
[%Si]0. As the slag-metal reaction proceeds, k
tends to increase with decrease of Si concentration.
The above experimental result could be explained
by employing a new concept that the zone of reaction
between Si and 0 is located within the metal-side
boundary layer. The location of the zone is sup-
posedly controlled by mass-transfer fluxes of oxygen
from the slag-metal interface to the reaction zone and
silicon from the bulk metal to the zone.
The slag-metal reaction (13) can be regarded as
Fig. 18. Relation between log [%Si] and time with various
[%Sl]0,59)
an oxidation reaction of a strong deoxidizer dissolved
in liquid metal. Therefore, the above study may be
generally related to kinetic mechanisms of reactions
between molten slag and molten metal containing
solute elements which interact strongly with oxygen.
Pluschkell et a1.60~investigated kinetics of oxidation of
aluminum in steel melts by iron and manganese oxides
in slag during Ar-injection stirring. They analyzed
the rate data on the basis of the assumption that a re-
action zone was formed within the metal-side bound-
ary film. Though the paper of Pluschkell et al. lacks
detailed examinations on the reaction zone, the paper
should be regarded as a notable report that proposed
a highly interesting problems on slag-metal reactions.
2. Slag-Molten Iron Reactionswith Formation of CO
The reactions treated below are concerned with
slag-molten iron reactions under reducing conditions.
One finds that even apparently simple reactions are
complicated by the occurrence of side reactions and
formation of CO. Extensive studies have been made
on the kinetics of desulfurization of carbon-saturated
 Transactions ISIJ, Vol. 28, 1988 (255)

iron and reduction of iron oxide in slag by carbon in ence of a gas film at the slag-metal interface. It is
iron. proposed that the overall reaction of Eq. (15) takes
A very noteworthy paper was published in 1956 by place as the sum of the following reactions:
Ramachandran et a1.61) in which the rate of sulfur
transfer between carbon-saturated iron and oxide slag FeO (in slag) + CO (g) = Fe + C02 (g)
was measured with concurrent measurement of CO (16)
evolution. The most salient result is that, while sulfur and
transfer from the metal to the slag phase is occurring, C02 (g)+C = 2C0 (g) (17)
the silicon content of the metal initially decreases to
that below the equilibrium value and iron is initially At iron-oxide contents below about 2.5 % the rate-
transferred to the slag but again tends to decrease. controlling step is the chemical reaction represented
Ramachandran et al. interpreted their results in terms by Eq. (17), while at higher iron-oxide contents the
of an electrochemical mechanism. Hemptinne et a1.62) rate-controlling step is that of Eq. (16). Sommerville
gave an explanation to the result of Ramachandran et al. showed reasonable agreement between the value
et a1.61) by postulating the potentials and electrical of the rate constant of the iron-oxide reduction at
currents flowing across the slag-metal interface. Oh- lower iron-oxide contents and that of decarburization
tani63) and other authors have proposed explanations of molten iron obtained by Samnand Belton35)referred
of kinetics of slag-metal reactions using electrochem- to in Chap. III of the present paper. It appears that
ical theories. However, as Kawai64) pointed out, the the agreement mentioned above has provided a strong
electrochemical theory does not produce a fruitful ex- evidence in support of the reaction mechanism pro-
planation because of lacking in the knowledge on posed by Sommervi.lle et al.
polarization curves of single reactions.
Recently, Robertson et al.65) has developed a gen- 3. Rate of Mass Transfer betweenMolten Slag and Metal
eral kinetic model for multicomponent slag-metal and underGas InjectionStirring
slag-metal-gas reactions, assuming that the rates are In recent years, the kinetics of reactions between
controlled by multicomponent transport processes in slag and molten iron with gas injection in steel refining
the metal and slag phases. The model has given a processes have become of increasing interest to the
reasonable simulation of the sulfur transfer studied by metallurgists. Previously studies were made by Rich-
Ramachandran et a1.61) ardson and co-workers on elucidating the fundamen-
Mori et al.66) have made a study on the rate of tal relation between the slag-metal reaction rate and
desulfurization of liquid iron and iron-carbon alloys gas injection stirring conditions with using model re-
by CaF2-based slags. During desulfurization of iron action systems at low temperatures, i.e., aqueous solu-
the concurrent transfer of iron, similar to the phe- tion-amalgam system68'70'71) and molten salt-molten
nomenon found by Ramachandran et al., was ob- lead system.69-71)From the practical viewpoint, mod-
served. The results could be explained by a modified el studies have been made frequently with using or-
mass transfer model in which CO gas evolution was ganic solvent-water system.72) This kind of model
assumed to be controlled by a chemical reaction and studies may produce questionable results for the ap-
the transfers of other components were controlled by plication to actual slag-metal systems because of the
mass transfer. low interfacial tension in organic solvent-water sys-
The above studies by Robertson et a1.65) and by tems.
Mori et al.66) have revealed that the phenomena in These years, model experiments have been done in
sulfur transfer between slag and metal phases first the author's laboratory to investigate the role of gas
observed in the middle of fifties by Ramachandran injection stirring in slag-metal reactions at high tem-
et al. could be explained reasonably after three decades peratures with using a molten slag-Cu system where
by mass transfer models. physical properties are similar to those of slag-molten
Kinetics of the reduction of iron oxide from molten iron system.73) Concerning this slag-Cu reaction sys-
slaps by carbon in iron is interesting practically in tem mention has been made in Sec. IV. 1. The ex-
connection with reactions occurring in the hearth plored reaction is oxidation of Si by FeO (Eq. (13) )
zone in the blast furnace. In a paper most recently at 1250°C, taking place under the condition of rate-
published by Sommerville et a1.,677 it is pointed out controlling by Si transport in the metal phase. The
that in almost all previous studies the experimental slag-metal bath was stirred by Ar gas injected through
systems were rather complicated for obtaining clear- a nozzle located at the crucible bottom. The gas-
cut conclusions for the reaction mechanism. This flow rate (Vg), crucible diameter (dr) and metal depth
was mainly due to the presence of graphite. Hence, (hM) were varied.
in the work by Sommerville et a1.67) the reaction sys- Figure 19 shows typical experimental results for the
tem was selected so that only the simple reaction relation between the logarithm of the Si concentra-
tion and time. Here, h81is the slag depth and Vg is
FeO (in slag) + C = Fe + CO (g) ............(15)
expressed for the conditions of 1250°C and 1 atm
proceeded. The reduction rate was measured by the pressure. All the data are represented by linear lines
observation of the pressure change in the system. In predicted from Eq. (14). From the slope of the linear
attempting to explain the reaction mechanism, they line the apparent mass transfer coefficient of Si, ks1, is
devoted special attention to the possibility of the pres- calculated.

Review
(256) Transactions ISIJ, Vol. 28, 1988

Fig. 19. Typical relation between log [%Si]

and time.73~

Fig. 20. Relation between ks1 and gas-flow rate (d~= Fig. 21. Relation between ks1 and gas-flow rate (d~=
4 cm).73) 7.5 cm).")

Figures 20 and 21 present the relation between ks1

and Vg for d~=4 and 7.5 cm, respectively. The de-
pendence of ks1on Vg at constant d~ changes at transi-
tional gas-flow rates denoted by Vg and Vg. A
similar result is obtained for d~=3 cm. The whole
range of gas-flow rate explored is divided into three
regions :
(i) Region I (Vg< Vq*) where ksiocV2,
(ii) Region I I (V g < Vg< Vg*) where the effect of
the increase in Vg on ks1is considerably smaller
than in Region I, and
(iii) Region III (Vg> Vg*) where the extent of the
increase in ksi with Vgincreases again.
From the experiments of varying metal depth, in-
teresting results presented in Fig. 22 are obtained,
where hI is the distance between the slag-metal inter-
face and the nozzle tip. Here, hl=hM-0.5 (cm). As Fig. 22. Relation between apparent mass transfer coefli-

seen from Fig. 22, ks1is proportional to h112below a cient of Si, ks1, and injection depth of metal phase,

transitional depth, Ii?, while it becomes independent hI.74j

of h1 at hI>hj.
Another phenomenon almost unexpected is that in very complicated. Hirasawa et a1.74~ have made ana-
Region II ks1 increases with increasing h81, while in lytical approach to the metal-side mass transfer in
Region I ks1is independent of h81(Fig. 23). Region I by use of the theory of turbulence phe-
One could realize, from the above presentation of nomena developed by Davies.75~ This theory has pre-
the experimental data for the mass transfer coefficient viously been applied to the problem of slag-metal
(ks1), that the nature of mass transfer between metal mass transfer by Robertson and Staples.70~ However,
and slag phases affected by gas injection stirring is the assumption made by Hirasawa et al. for " the scale

Fig. 23. Relation between ks; and slag depth,
of energy containing eddies " is utterly different from
that by Robertson et al.
Hirasawa et a1.74~ have developed equations for the
metal-side mass transfer coefficient as function of gas
injection stirring conditions. The theoretical equa-
tions are rearranged to dimensionless equations.
Hirasawa et al. have obtained dimensionless equa-
tions for the four cases of gas injection stirring condi-
tions: Vg<Vg and h1<hI, Vg<Vg and hI>hI, Vg>
Vg and h1<h, and Vg> Vg and h1>h~ . As an ex-
ample, the correlation of mass transfer data at Vg< Vg
and hI<hI is presented in Fig. 24. The mass transfer
data obtained from model studies for molten slag-Cu
reaction system of Si oxidation at 1250°C and the
available results of model studies at low temperatures
(aqueous solution-amalgam system at room tempera-
ture and molten salt-molten Pb system at 450°C) are
correlated successfully by one theoretical equation.
It is found that the mass transfer data of practical
ladle desulfurization refining could be explained rea-
sonably by the present correlation equation.76)
V. Kinetics of Solid-Liquid Metal Interactions
1. Scrap Melting
The rate of scrap melting has important connec-
tions with end point temperature control in LD steel-
making furnace and power consumption in electric
furnace steelmaking processes. This problem has
aroused considerable attention early in western coun-
tries.77) Recently, in Japan scrap melting rate is dis-
cussed in developing new LD processes utilizing a
large amount of scrap.
From academic point of view, scrap melting pro-
vides an interesting phenomenon in which simul-
taneous heat and mass transfers occur. Mori and
Nomura78~on the basis of the concept of transfer phe-
nomena, developed a mathematical model for scrap
melting in the steelmaking process. Steady state
equations are postulated for heat and mass transfer in
the boundary layer between solid and liquid. Heat
conduction in the solid is expressed by an unsteady
state equation. The values of the thickness of the
boundary layer and the heat transfer coefficient are
Transactions ISIJ, Vol. 28, 1988 (257)
Fig. 24. Dimensionless correlation of mass transfer data at
hsi.74) Vg<Vg and hI<hj.74)
V 1
Fig . 25. Solidification of pig iron on cold scrap.7s)
assumed from the results of fundamental studies by
Nomura and Mori.7s~
The process of scrap melting can be broken into
two stages. In the first stage, some molten iron
freezes on the scrap surface and then the frozen iron
melts back until the original interface appears to the
molten bath. As suggested from Fig. 25, the time of
solidification of iron on cold scrap is rather short.
In the second stage, melting of scrap proceeds first
with carburization at the scrap surface and then with
subjecting of the scrap to the bath of temperature
higher than the true melting point of the scrap. Mori
and Nomura, assuming that the time for the first stage
is negligible, calculated the relation between scrap
melting ratio and time (Fig. 26). It is indicated that
the model calculation gives a general agreement with
practical data in the case of simple form of scrap.78~
The feature of the phenomena implied in Fig. 25
have an important meaning in the kinetics of melting
dissolution of deoxidizers, i.e., A1,for steel. This field
has been extensively examined by Guthrie.80~
2. Dissolution of Solid Iron in a Carbon-saturatedLiquid
Iron with Evolutionof CO
The kinetics of solution of solids into liquid accom-
(258) Transactions ISIJ, Vol. 28, 1988

panied with evolution of gas is an important and cylindrical specimen was stationary in one series of
interesting problem and has been studied first by experiments; in another series it was rotated.
Mori and Sakuraya.81) The experiments consisted of It has been well established that the rate-control-
measuring the rate of dissolution of iron cylinders con- ling step in the isothermal dissolution of solid iron into
taining various amounts of oxygen immersed in the liquid iron-carbon alloys is mass transfer in the liquid-
melt of carbon-saturated iron. During dissolution side boundary layer. During dissolution of specimens
CO was evolved from the reaction between carbon in containing oxygen, CO bubbles are considered to be
the melt and oxygen in the iron specimen. The produced in the boundary layer. Therefore, the ef-
fect of bubble formation on the mass transfer rate will
be reflected on the value of mass transfer coefficients.
In the case of stationary dissolution, oxygen in the
iron specimen, that is, the evolution of CO was found
to have a marked effect on the dissolution rate. In
Fig. 27, the mass transfer coefficient, k, is plotted
against the rate of CO evolution per unit area of the
specimen surface, 'co. The highest value of k at
1400°C are 73 times as large as the lowest value at
1200°C. At lower temperatures, k increases with Vco
to a power of 0.3. At higher temperatures, k is pro-
portional to VcoS. This phenomenon is shown to be
analogous to the mass transfer at a gas evolving elec-
trode.
Figure 28 is the data for rotational dissolution at
1 250°C. At lower rpm the mass transfer coefficient
is controlled mainly by the extent of CO evolution.
Fig. 26. Typical relations between scrap melting ratio and At higher rpm (rpm>250), the effect of rotation be-
time.79~ comes predominant. Similar relationship has been
observed in the reduction of rotated solid Cr203 by
liquid Fe-Cr-C alloys as mentioned in the next sec-
tion.
The present result provides a reasonable explana-
tion on the melting of prereduced iron particles in an
electric arc furnace in which the utilization efficiency
of electric power decreases with the metallization ratio
of the charged material.82~
3. Reductionof Cr203 by Carbon Dissolvedin Liquid Fe-
Cr Alloys
Knowledge on the rate controlling mechanism of
reduction of Cr203 by carbon is of great importance
in understanding events occurring in the AOD pro-
Fig. 27. Mass transfer coefficient res. CO evolution rate for cess of stainless steel refining and the smelting reduc-
stationary dissolution at various temperatures.81~ tion of chromite ore. The kinetics of Cr203 reduc-
tion has been studied by Fruehan,83~ Sevinc and
Elliott,84~and Suzuki and Mori.85~
Suzuki and Mori85~measured the rate of reduction
of rotated Cr203 cylinder by carbon dissolved in Fe-
10%Cr melt at 1 580°C.
Figure 29 shows the relation between dissolution
rate of the cylinder and rotational speed at various
carbon contents. At the initial carbon concentration
of 0.3 %, where evolution of CO bubbles from the
cylinder-melt interface did not occur, dissolution rate
increases gradually with increasing rotational speed.
At carbon contents above 0.3 %, CO bubbles were
observed to evolve. Here, the effect of rpm becomes
to a lesser extent with increasing carbon content.
For the dissolution of rotating cylinder into liquid
without gas evolution, the mass transfer coefficients,
Fig. 28. Mass transfer coefficient res. rpm for rotational dis- in terms of dimensionless correlations, are compared
solution of iron cylinders of various oxygen contents with those for various non-metallic and metallic sys-
at 1250°C.81~ tems (Fig. 30). From the figure, it is clear that ex-
 Transactions Is", Vol. 28, 1988 (259)

Fig. 29. Relation between dissolution rate of sample and

rotational speed at various carbon concentra-
tions.85)

cept for the two points in the lower range of Re, the Fig. 30. Dimensionless correlation for dissolution of rotat-

data for the Cr203 reduction are in reasonable agree- ing cylinder into liquid phase.85)

ment with those for the other systems.

The overall reaction expressed by lems concerning non-metallic inclusions will become
increasingly important. Carefully designed experi-
Cr203+3C = 2C+3CO (g) ............(18)
ments should be done to investigate the kinetics of
is represented by the following sequential equations: removal of non-metallic inclusions from molten metal.
For this research, high temperature model studies are
Ca203 (s) = 2Qr+30 ..................(19) likely to produce fruitful results. Interfacial phe-
0 +C = CO (g) ........................(20) nomena should be much more taken into considera-
tion in the kinetic studies of metallurgical systems.
For the two reaction steps, various rate-controlling Effects of interfacial resistance on the rate of nitrogen
steps are postulated. Comparing the mass transfer removal from molten iron mentioned in the present
coefficients calculated on the basis of the various
paper is a typical example. In view of practical
postulations, the author has arrived at the conclusion needs for improving production processes and devel-
that the rate of Cr203 reduction is controlled by the oping new processes, a great deal of research in pro-
rate of mass transfer of oxygen across the boundary cess science should be more promoted in academic
layer in the melt at the solid-liquid interface. This circles.
conclusion is qualitatively the same as that obtained
by Sevinc and Elliott.84~ However, their data do not Acknowledgement
agree with those shown in Fig. 30. Fruehan83~ as- The author wishes to thank Professor Masamichi
sumed that the rate was controlled by mass transfer Sano, Department of Metallurgy, Nagoya University,
of carbon in the melt. It is difficult to justify this for the help in preparing the manuscript of this paper.
conclusion because of the scatter in his experimental
result.
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