Simulation of Primary-Slag Melting Behavior in the Cohesive

Zone of a Blast Furnace, Considering the Effect of Al2O3,

FetO, and Basicity in the Sinter Ore
MITSUTAKA HINO, TETSUYA NAGASAKA, AKITOSHI KATSUMATA, KEN-ICHI HIGUCHI,
KAZUYOSHI YAMAGUCHI, and NORIMITSU KON-NO

The alumina content in the iron ore imported to Japan is increasing year by year, and some problems
in blast furnace operation, due to the use of the high-alumina-containing sinter, have already been
reported. In order to clarify the mechanism of the harmful effect of alumina on the blast furnace
operation, the behavior of the primary melt, which is formed in the sinter at the cohesive zone of the
blast furnace, has been simulated by dripping slag through an iron or oxide funnel. The effects of
basicity, Al2O3, and FetO contents in the five slag systems on the dripping temperature and weight
of slag remaining on the funnel have been discussed. It was found that the eutectic melt formed in
the sinter would play an important role in the dripping behavior of the slag in the blast furnace
through the fine poreosity of the reduced iron and ore particles. Al2O3 increased the weight of the
slag remaining on the funnel, and its effect became very significant in the acidic and low-FetO-
containing slag. It was estimated that the increase of the weight of the slag remaining on the funnel
by Al2O3 in the ore could result in a harmful effect on the permeability resistance and an indirect
reduction rate of the sinter in the blast furnace.

I. INTRODUCTION is generally estimated that the alumina in the sinter would

DUE to the lack of high-grade iron-ore resources in the
world, impurities such as phosphorus, crystalline water, and
alumina in the iron ore imported to Japan are being
increased,[1] and the change of iron-ore composition is
resulting in some problems for the blast furnace operation in
Japanese ironmaking companies.[2,3,4] Actually, it is reported
that a small increase in the amount of alumina could exhibit
negative effects on the gas-permeability resistance and the
reducibility of the iron-ore sinter in the lower part of the blast
furnace, and it also increases the slag volume. In addition, the
increase of alumina in the ore could also cause harmful
effects in the iron-ore sintering process such as the decrease
of producibility, yield strength, and quality of the sintered
product.[2,3,5] Since all of the iron ore used by Japanese
ironmaking companies is imported from overseas (from Aus-
tralia, Brazil, and so on), the problems caused by the lower-
grade ore should be solved as soon as possible.
The true mechanism of the harmful effect of alumina on
the blast furnace operation was not known up until now,
due to the very complex phenomena in the blast furnace. It
MITSUTAKA HINO, Professor, and TETSUYA NAGASAKA, Associ-
ate Professor, are with the Department of Metallurgy, Graduate School
of Engineering, Tohoku University, Sendai 980-8579, Japan. AKITOSHI
KATSUMATA, formerly Graduate Student, Department of Metallurgy,
Graduate School of Engineering, Tohoku University, is Researcher,
Research Laboratories, Nippon Yakin Kogyo Co. Ltd., Kawasaki 210-0823,
Japan. KEN-ICHI HIGUCHI, Senior Researcher, and KAZUYOSHI
YAMAGUCHI, Chief Researcher, are with the Ironmaking Process, Process
Technology Research Laboratories, Technical Development Bureau, Nip-
pon Steel Corporation, Futts 293-8511, Japan. NORIMITSU KON-NO,
formerly General Manager, Ironmaking Process, Process Technology
Research Laboratories, Technical Development Bureau, Nippon Steel Cor-
poration, is Board Director, Research and Development Division, Nippon
Shokubai Co. Ltd., Osaka 541-0043, Japan.
Manuscript submitted January 8, 1998.
play an important role, mainly in the behavior of the primary
melt formed in the sinter during the reduction. The primary
melt is formed in the iron-ore sinter near the softening or
cohesive zone of the blast furnace. It is reported that the
large amount of alumina is concentrated in the primary melt,
even if the increment of alumina content in the ore is small,
for example, from 1.5 to 1.8 pct.[6] Therefore, it is reasonable
to consider that the small amount of increase of alumina in
the iron ore would result in a large effect on the behavior
of the primary melt. If this primary melt could penetrate the
microporosity of the sinter or become trapped among gaps
in the sinter, the gas-permeability resistance in the lower
part of the furnace would increase and the reducibility of
the sinter would decrease due to the smaller effective sur-
face area.
According to the aforementioned background, the present
authors have studied the effect of gangues, particularly alu-
mina, on the dripping behavior of the primary melt in the
lower part of the blast furnace. It may be difficult to know
the precise composition of the primary melt, its reduction,
and its penetration behavior in the practical blast furnace.
The authors have developed a new method using the thermo-
gravimetric technique to simulate the dripping behavior of
slag melt from an iron or oxide funnel. The synthesized
FetO-containing slag, which is assumed to be the primary
melt, was heated and dripped from the funnel to simulate
the dripping behavior of the slag from the reduced metallic-
iron or unreduced ore particles. The dripping temperature,
the amount of slag remaining on the funnel, the composition
of the slag dripped from the funnel, the slag remaining on
the funnel, and the coexisting oxide phases with the slags
have been investigated as a function of the FetO and alumina
content and the basicity of the initial slag. Section IV
attempts to explain the hold-up mechanism of the slag on

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 30B, AUGUST 1999—671


Fig. 1—Compositional planes of FetO-Geh-C2S, FetO-Geh-CS, FetO-C2S-
CS, FetO-Ano-CS, and FetO-Geh-Ano pseudoternary systems in the FetO-
CaO-SiO2-Al2O3 system.
the funnel, based on the wettability of the funnel by the
slag, in the present work.
II. EXPERIMENTAL
A. Slag Systems
The practical iron-ore sinter used in the blast-furnace pro-
cess consists of at least six components such as FeO-Fe2O3-
CaO-SiO2-Al2O3-MgO, and it is difficult to obtain precise
information on the phase equilibria in such a complex oxide
system. The composition of the primary melt formed in the
iron-ore sinter during reduction in the blast furnace, and its
co-existing solid-oxide phases, are also unknown. Moreover,
the concentration of iron oxide in the sinter ore and the
temperature are not constant during the reduction process
in the blast furnace, so that thermodynamic estimation of
the composition of the primary melt and its co-existing solid-
oxide phases are also very difficult. Therefore, it is almost
impossible to perform a precise simulation of the behavior
of the primary melt in the blast furnace. On the other hand,
it is reported[6] that the actual composition of the primary
melt in the sinter is found to be close to the iron oxide–
Gehlenite (2CaO ? SiO2 ? Al2O3, hereinafter called “Geh”)
system saturated with Monocalcium-silicate (CaO ? SiO2,
hereinafter called “CS”) or Dicalcium-silicate (2CaO ? SiO2,
hereinafter called “C2S”). Since phase diagrams of these
pseudoternary systems are available in the literature,[7] it is
convenient to use these slag systems to simulate the behavior
of the primary melt. Therefore, the authors have first
assumed the FetO-Geh-C2S and FetO-Geh-CS slags to be
the primary melt, and experiments have been conducted by
dripping these slags through an iron, CaO, or MgO funnel.
In order to study the effects of FetO and alumina content
and basicity on the dripping behavior of slag in a wide
compositional range, experiments were extended to FetO-
C2S-CS, FetO-Anorthite (CaO ? 2SiO2 ? Al2O3, hereinafter
called “Ano”)-CS, and FetO-Geh-Ano systems. Phase dia-
grams of these three additional pseudoternary systems are
also available in the literature.[7,8]
Figure 1 illustrates the compositional planes of five kinds
of slag systems in the FetO-CaO-SiO2-Al2O3 compositional
672—VOLUME 30B, AUGUST 1999
tetrahedron investigated in the present work. As seen in
Figure 1, these five slag systems can cover almost the whole
composition range of the practical iron-ore sinter, so that
it is possible to effectively determine the effect of sinter
composition, such as FetO, Al2O3, and and basicity, on the
dripping behavior of the primary melt in the blast furnace.
It is also possible to simulate the effect of the degree of
reduction of the iron-ore sinter, or of the gangue-minerals
variation in the ore, on the behavior of the primary melt by
changing FetO contents at constant gangue contents in the
slag specimen, and vice versa. The effect of Al2O3 on the
dripping behavior of the slag at constant basicity (CaO/SiO2 5
1.87 in mass pct ratio) in the FetO-Geh-C2S slag (system
1), as well as that of basicity in an Al2O3-free FetO-C2S-CS
slag (system 3) and in a high-Al2O3-content FetO-Geh-Ano
slag (system 5), can be investigated at given FetO contents
in the present work. The Al2O3 content increases with
increasing basicity in the FetO-Geh-CS slag (system 2) or
with decreasing basicity in the FetO-Ano-CS slag (system
4) by exchanging CS for Geh or Ano under a constant FetO
content. The content of FetO in each system was changed
under a constant mass ratio with the other two compounds,
such as Geh/(C2S 1 Geh), Geh/(CS 1 Geh), C2S/(CS 1
C2S), Ano/(CS 1 Ano), and Geh/(Ano 1 Geh), which is
defined as the “gangue ratio” (hereinafter called “GR”). The
effect of the GR was investigated under given FetO contents
at approximately 20, 40, and 63 mass pct. The experimental
slag systems examined in the present work and their initial
compositions are listed in Table I.
Slag samples were prepared from reagent-grade chemicals
such as CaCO3, Al2O3, SiO2, Fe, and Fe2O3. CaCO3 was
first calcined in a Pt crucible at 1273 K under an air stream to
produce CaO. FetO was synthesized by sintering equimolar
amounts of Fe and Fe2O3 powder for 6 hours in an iron
crucible at 1373 K, under a purified Ar stream. Then, these
materials were crushed into a fine powder, well mixed at the
determined composition, and premelted in an iron crucible at
1673 K under a purified Ar stream. FetO-free slags were
premelted in a Pt crucible at 1873 K in air. Premelted slag
samples were crushed, pressed into a tablet shape, and used
for the dripping experiment. The slag composition was cho-
sen in the homogenous liquid region at 1673 K, based on
the available phase diagrams.[7,8,9] Four grams of slag sample
were used in each experiment, except for a few of the runs.
B. Funnel
Figure 2 illustrates the funnel used in the present work.
The gradient of the inner wall of the funnel is 55 deg, and
the funnel has a small hole 4 mm in diameter at the bottom,
which simulates the porosity of the iron-ore sinter.[10] Iron
was used as the funnel material in order to simulate the
dripping behavior of the primary melt through the porosity
of the reduced iron, while pure oxide was used as a funnel
material to simulate the porosity of unreduced sinter ore. In
some parts of the experiment in the FetO-Geh-C2S system,
CaO was used as the funnel material in order to maintain
the slag composition as C2S saturation. MgO was also used in
some experimental runs in the FetO-Geh-CS system, because
MgO seemed to be an almost inert material due to its very
small solubility in FetO-CaO-SiO2-Al2O3 slag, as pointed
out by the authors.[11]
METALLURGICAL AND MATERIALS TRANSACTIONS B
 Table I. Results of the Present Experimental Runs

Hold-up Initial Slag Composition in Mass Pct Liquid Ratio at Eutectic

Number Dripping Temperature (8C) (g) FeO C2S Geh GR Al2O3 Basicity Temperature (Pct)
(a) System 1 (FetO-C2S-Geh system)
101 1268 1.50 40.5 31.2 28.3 0.48 10.5 1.87 71.8
C 1255 1.87
102 1289 1.18 51.6 23.5 24.9 0.51 9.3 1.87 92.2
C 1250 1.41
103 1235 0.89 61.1 21.8 17.1 0.44 6.4 1.87 75.5
C 1265 1.18
107 1280 1.06 65.8 34.2 0 0 0 1.87 89.9
C 1290 1.34
108 1260 1.12 64.8 24.9 10.3 0.29 3.8 1.87 45.5
C 1275 1.20
111 1256 0.99 60.8 10.9 28.3 0.72 10.5 1.87 61.3
C 1240 1.09
112 1237 0.96 60.8 0 39.2 1.00 14.6 1.87 97.1
113 1219 1.34 44.8 23.1 32.1 0.58 11.9 1.87 78.7
120 1263 0.96 55.8 0 44.2 1.00 16.4 1.87 89.5
121 1220 1.28 47.9 0 52.1 1.00 19.4 1.87 79.9
123 1247 1.49 42.3 0 57.7 1.00 21.5 1.87 68.1

Hold-up Initial Slag Composition in Mass Pct Liquid Ratio at Eutectic

Number Dripping Temperature (8C) (g) FeO CS Geh GR Al2O3 Basicity Temperature (Pct)
(b) System 2 (FetO-CS-Geh system)
201 1215 1.88 0 69.2 30.8 0.31 11.5 1.08 82.0
M 1230 1.30
202 1188 1.57 9.7 62.5 27.8 0.31 10.3 1.08 35.6
M 1160 0.63
203 1185 1.10 20.8 55.5 23.7 0.30 8.8 1.08 75.3
M 1177 1.18
204 1160 1.04 32.0 45.8 22.2 0.33 8.3 1.09 3.0
M 1180 0.71
205 1295 0.65 20.4 79.6 0 0 0 0.93 62.2
M 1320 0.23
206 1178 0.92 20.8 70.0 9.2 0.12 3.4 0.98 76.0
207 1157 1.60 21.4 46.4 32.2 0.41 12.0 1.15 75.7
M 1200 1.61
208 1154 1.86 19.8 40.0 40.2 0.50 14.9 1.21 70.7
M 1160 1.54
209 1245 0.35 61.9 38.1 0 0 0 0.93 68.6
M 1233 0.28
211 1173 0.45 63.3 26.2 10.5 0.29 3.9 1.07 61.3
M 1162 0.35
212 1179 0.82 40.1 40.3 19.6 0.33 7.3 1.09 90.0
213 1188 0.96 39.8 30.1 30.1 0.50 11.2 1.21 67.3
214 1215 1.46 39.7 15.1 45.2 0.75 16.8 1.46 32.7
215 1221 0.63 41.3 58.7 0 0 0 0.93 66.7
112 1237 0.96 60.8 0 39.2 0.01 14.6 1.87 98.3
M 1234 0.88

Hold-up Initial Slag Composition in Mass Pct Liquid Ratio at Eutectic

Number Dripping Temperature (8C) (g) FeO CS C2S GR Al2O3 Basicity Temperature (Pct)
(c) System 3 (FetO-CS-C2S system)
303 1125 0.91 22.6 55.1 22.3 0.29 0 1.13 20.8
304 1142 0.61 45.1 39.9 15.0 0.27 0 1.12 86.6
305 1131 1.20 10.6 64.1 25.3 0.28 0 1.13 41.0
310 1253 0.56 62.5 26.7 10.8 0.29 0 1.13 59.8
312 1150 0.92 22.6 64.1 13.3 0.17 0 1.05 79.7

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 30B, AUGUST 1999—673

 Table I. Continued

Hold-up Initial Slag Composition in Mass Pct Liquid Ratio at Eutectic

Number Dripping Temperature (8C) (g) FeO CS Ano GR Al2O3 Basicity Temperature (Pct)
(d) System 4 (FetO-CS-Ano system)
403 985 2.06 34.9 36.9 28.2 0.43 10.3 0.75 —
404 1067 1.53 22.7 47.5 29.8 0.39 10.9 0.77 —
405 985 3.16 22.7 31.0 46.3 0.60 17.0 0.67 —
406 1219 1.60 0 60.1 39.9 0.40 14.6 0.77 —
407 1074 0.85 23.3 61.2 15.5 0.20 5.7 0.85 —
408 1088 1.56 15.3 50.8 33.9 0.40 12.4 0.77 —
409 1123 0.49 61.0 24.2 14.8 0.38 5.4 0.78 —

Hold-up Initial Slag Composition in Mass Pct Liquid Ratio at Eutectic

Number Dripping Temperature (8C) (g) FeO Geh Ano GR Al2O3 Basicity Temperature (Pct)
(e) System 5 (FetO-Geh-Ano system)
501 1348 0.61 0 46.9 53.1 0.47 36.9 0.90 —
502 1181 2.02 23.8 45.4 30.8 0.60 28.2 1.07 —
507 1165 1.78 33.0 32.1 34.9 0.48 24.7 0.91 —
508 1185 2.67 21.4 36.7 41.9 0.47 29.0 0.90 —
511 1173 1.34 64.2 6.9 28.9 0.19 13.2 0.62 —
512 1130 0.94 63.8 17.0 19.2 0.47 13.4 0.90 —
514 1157 0.73 64.7 20.9 14.4 0.59 13.0 1.06 —
In the first column, C and M denote the runs with CaO and MgO funnels, respectively; the others are with iron funnel.
C2S 5 2CaO ? SiO2, Geh 5 2CaO ? SiO2 ? Al2O3, CS 5 CaO ? SiO2, and Ano 5 CaO ? 2SiO2 ? Al2O3.
GR 5 Geh/(C2S 1 GeH) for system 1, Geh/(CS 1 Geh) for 2, C2S/(CS 1 C2S) for 3, Ano/(CS 1 Ano) for 4, and Geh/(Ano 1 Geh)
for 5 in mass.
Initial slag mass is 4 g.

Fig. 2—Schematic diagram of the funnel.

C. Apparatus and Procedure

1. Dripping experiment
A vertical type of electric resistance furnace was used
for the dripping experiment. Figure 3 shows a schematic
illustration of the experimental apparatus. A double-spiral
type of SiC was used as a heating element. The reaction
tube was made of Mullite (42 mm o.d., 35 mm i.d., and
700-mm long). The temperature was monitored by a Pt/Pt-
13 pct Rh thermocouple in the reaction tube. The temperature
of the furnace was controlled automatically with a Proportion Fig. 3—Schematic diagram of the apparatus for the dripping experiment.
Integration Differentiation (PID) unit. The weighed slag
sample (typically 4 g), with a tablet shape, was put on the

674—VOLUME 30B, AUGUST 1999 METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 4—Schematic diagram of the apparatus for the surface tension mea-
surement of slag melt.

weighed funnel, which was suspended by Mo wire from the

electrobalance set above the furnace, as shown in Figure 3.
The length of the Mo wire was adjusted to keep the location
of the funnel in the hot zone of the furnace. After suspending
the funnel and setting a weighed iron dish for collecting
dripped slag just below the funnel, the inside of the reaction
tube was evacuated, and then the sample was heated at the
constant rate of 5 8C/min under a purified Ar stream of
approximately 100 cm3/min. The weight change of the sam-
ple was continuously monitored by the thermobalance, and
the temperature of the slag dripping from the funnel’s hole
was detected by a large discontinuous weight change. It was
confirmed in the preliminary experiments that no additional
dripping phenomena occurred at a temperature higher than
that at which the first dripping occurred, within the present
experimental-temperature range (approximately ,1400 8C).
Therefore, this temperature at which a large discontinuous
weight change was observed was defined as the “dripping
temperature.” The dripping temperature was calibrated by
the thermocouple in contact with the iron dish, based on
the temperature profile of the furnace determined in the Fig. 5—Effects of FetO and gangue ratio, GR, on the dripping temperature
preliminary blank test. After detecting the dripping tempera- of FetO-Gehlenite-Moncalciumsilicate slag (system 2).
ture, the sample was cooled to room temperature at 5 8C/
min in the furnace, under Ar steam, and the funnel and
iron dish were weighed to determine the weight of the slag sample was heated at a constant rate of 2 8C/min in the Ar
remaining on the funnel. The weight of slag remaining on stream. When the slag sample was melted and a liquid droplet
the funnel after dripping is defined as “holdup” in this article. was formed on the iron substrate, an image of the liquid
The compositions of the slag which dripped from the funnel slag was taken by a high-quality digital still camera (DS-
and the slag which remained on the funnel were determined 505, Fuji Film Co. Ltd., Tokyo, Japan) through a quartz
by wet chemical analysis. Some slag samples were supplied glass window set at one of the end caps. After the temperature
for X-ray diffraction analysis (XRD) to identify the oxide reached 1350 8C, at least ten image pictures were taken over
phases coexisting with the melt. 2 hours. The image of the slag droplet was analyzed by the
2. Surface-tension measurement computer-aided system to evaluate the surface tension and
The present authors considered that the hold-up phenome- contact angle of the slag to the solid iron. Details of the
non of slag on the funnel would be governed by the wettabil- principle analytical method and the derivation of surface
ity of the funnel by the slag. Therefore, the surface tension tension and contact angle from the liquid-shape profile have
of the slag remaining on the funnel was observed in the been described elsewhere.[12,13,14]
present work. The Sessile-drop method was employed to
measure the surface tension of the melt on the iron substrate.
III. RESULTS
Figure 4 is the schematic illustration of the apparatus used
for the surface-tension measurement. A horizontal-type SiC Experimental results for the dripping temperature and
resistance furnace was used. The reaction tube was sealed holdup of the slag on the funnel are summarized in Table I.
at both ends by water-cooled brass caps. Approximately 1
g of slag sample, which was pressed into a tablet shape, was
A. Dripping Temperature
set on the thin electrolytic iron disk (35 mm in diameter and
2-mm thick), which was carefully kept horizontal. After Figure 5 shows a typical example of the effect of FetO
purging the inside of the reaction tube with purified Ar, the or GR on the dripping temperature from the iron funnel hole.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 30B, AUGUST 1999—675

These were observed in the FetO-Geh-CS system (system 2).
The dripping temperature under a fixed GR and constant
FetO content are almost constant, except for the Geh-CS or
FetO-CS pseudobinaries. In Figure 5, the liquidus tempera-
ture estimated from the phase diagram[7] is drawn as a dashed
line. It is clear from Figure 5 that the dripping temperature
is much lower than the liquidus temperature. A similar trend
is observed in other slag systems. That is, the dripping of
slag from the funnel could occur even at a lower temperature
than the completely melted temperature (liquidus tempera-
ture). The observed dripping temperatures are found to be
very close to their corresponding eutectic temperatures,
which are shown as solid lines in Figure 5. This indicates
that the temperature at which the liquid phase starts to form
in the sample, such as the eutectic point, would be a very
important factor in controling the dripping behavior of the
primary melt of slag in the blast furnace.
The dripping behavior of the slag melt through the surface
of the unreduced ore phase should also be taken into account.
Therefore, a MgO funnel was also used in the experiment
of this slag system (system 2). The effect of slag composition
on the dripping temperature from the MgO funnel is also
plotted in Figure 5, for comparison to the results obtained
with the iron funnel. As seen in Figure 5, the dripping
of slag from the MgO funnel occurs at a slightly higher
temperature than that with the iron funnel, but this difference
is insignificant. Therefore, the dependence of dripping tem-
perature on the slag composition would be identical to that
obtained with the iron funnel, and the phenomenon is essen-
tially the same in both cases.

B. Slag Holdup
Fig. 6—Effect of FetO and gangue ratio, GR, on the slag holdup of FetO-
It was observed after the experiment that some amount Geh-CS slag (system 2).
of slag remained on the funnel, and, therefore, the effect of
slag composition on such hold-up behavior was also investi-
gated. The results are shown in Figure 6, which examined
the FetO-Geh-CS system (system 2) as a typical example.
The slag holdup on the funnel definitely decreases with
increasing FetO content under constant GR, while it
increases by exchanging Geh for CS, under a fixed FetO
content, in the initial slag. The results obtained by using the
MgO funnel are also plotted in Figure 6 for comparison.
The holdup of slag on the iron funnel is approximately 10
pct larger than that on the MgO funnel. It indicates that a
larger amount of slag tends to remain on the iron funnel
than on the MgO funnel. However, the dependence of the
slag holdup on the initial slag composition is completely
the same with both funnels.
Figure 7 shows the relation between initial slag weight
and the weight of remaining slag on the iron funnel after
dripping. The slag weight on the funnel after the dripping
experiment is independent of the initial slag weight and Fig. 7—Effect of the initial slag weight on the slag holdup with the iron
shows an almost constant value of about 1.2 g. It is, therefore, funnel observed in the FetO-Gehlenite-Moncalciumsilicate system (sys-
confirmed that the slag holdup on the funnel is an intrinsic tem 2).
value which would be determined by the geometry of the
funnel and physical properties of the slag, such as surface
tension, wettability, and so on. spreads widely toward the edge of the bottom surface of the
Figure 8 is one of the most typical out-views of the shape funnel. In contrast, the shape of suspended FetO-free slag
of the slag suspended from the bottom of the funnel. These is like a “teardrop.” The spread of FetO-free slag is much
photographs were taken of the FetO-Geh-Ano slag (system narrower, and the suspended length in the vertical direction
5) on the iron funnel. The suspended slag, initially containing is much longer, than that of the FetO-containing slag. It is
33 mass pct of FetO, has a hemispherical shape, and it estimated from the observation that the wettability of the

676—VOLUME 30B, AUGUST 1999 METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 8—View of the iron fuunel after the experiment in the FetO-Gehlenite-
Anorthite system (system 5).
funnel by the slag might be changed with slag composition
and that the slag holdup might be governed by the slag
wettability.
C. Composition of the Dripped and Remaining Slags
The compositions of the slag dripped from and that
remaining on the funnel were chemically analyzed and com-
pared to the available phase diagrams of the five slag systems
investigated in the present work. The state of some slags
after the experiment seemed to be inhomogeneous, in partic-
ular, that of the remaining slag. Some amount of very small
solid particles were sometimes found together with the liquid
phase on the upper surface of the funnel, so that the specimen
of the remaining slag for chemical analysis was taken from
the slag which penetrated into the pores of the funnel. The
sample of dripped slag was taken from near the bottom part
of the solidified slag in the iron dish, because the slag in
contact with the iron dish would be cooled most quickly.
The results of each slag system are presented in Figures 9
through 13. The slag compositions determined are projected
onto the phase diagram of each slag system. In these figures,
the closed circle, open circle, and shaded square denote the
initial, remaining and dripped slag compositions, respec-
tively. The compositions of the slag which dripped from the
funnel are mostly found to be very different from their initial
compositions, while the compositions of the remaining slag
are not so different. All of the dripped slag compositions
are very close to the eutectic points. For example, as seen
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 9—Experimental slag composition in FetO-Geh-C2S slag (system 1).
Numerical values denote run number.
in Figure 10 (system 2), the dripped slag compositions of
samples 203 and 208 are very close to their corresponding
eutectic point of Geh-CS-Olivine ((Fe,Ca)O ? SiO2, herein-
after called “Olv”), and those of samples 201 and 205 are
near the eutectic points of Geh-CS and CS-Olv, respectively.
An XRD analysis was made for slag sample 203, obtained
with the MgO funnel. Geh, CS, and Olv are detected in the
dripped slag, as shown in Figure 14, together with some
very weak unknown peaks, MgO, and metallic-iron peaks
which would be contaminated from the vessel or precipitated
during the cooling, whereas peaks of CS and Geh are in the
remaining slag.
Similar trends were also observed in the FetO-Geh-C2S,
FetO-C2S-CS, FetO-Ano-CS, and FetO-Geh-Ano systems.
That is, (1) the observed dripping temperature is much lower
than the liquidus temperature and almost agreed with the
eutectic temperature in the slag systems, (2) the dripped slag
composition is close to the eutectic composition, and (3) co-
existing oxide phases corresponding to the eutectic reaction
VOLUME 30B, AUGUST 1999—677

Fig. 10—Experimental slag composition in FetO-Geh-CS slag (system 2).
Key as in Fig. 9. Numerical values denote run number.
Fig. 11—Experimental slag composition in FetO-C2S-CS slag (system 3).
Key as in Fig. 9. Numerical values denote run number.
678—VOLUME 30B, AUGUST 1999
Fig. 12—Experimental slag composition in FetO-Ano-CS slag (system 4).
Key as in Fig. 9. Numerical values denote run number.
Fig. 13—Experimental slag composition in FetO-Geh-Ano slag (system
5). Key as in Fig. 9. Numerical values denote run number.
are detected in the solidified dripping slag melt. Such tenden-
cies are independent of the kinds of funnel materials. It is
deduced, according to these experimental findings, that the
melt of eutectic composition is first formed during the heat-
ing of the slag, and this primary melt is preferentially dripped
from the funnel and melt-saturated, with solid oxide com-
pounds remaining on the funnel. Accordingly, the eutectic
melt formed in the sinter ore would play an important role
in the dripping behavior or the slag melt in the blast furnace
or in the or hold-up phenomenon of slag among the reduced
iron or ore particles. If such a mechanism is reasonable, it
would be suggested that the control of the temperature at
which the primary melt is formed and its composition would
be very important tools for controling the reduction of iron-
ore sinter in the cohesive or dripping zone of the blast
furnace.
According to the phase diagrams and the experimental
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 14—X-Ray diffraction pattern of the slag samples remaining on the
MgO funnel and dripped from the MgO funnel.
results, the slag should contain some amount of solids,
together with liquid, at the dripping temperature. The liquid-
solid ratio in each slag at the dripping temperature can be
estimated from the phase diagram of each system at the
eutectic temperature using the lever rule, if the sample is
heated to keep it at the equilibrium state and the available
phase diagram is correct. The liquid ratios can be calculated
in this manner for systems 1 through 3. However, such a
consideration cannot be applied to systems 4 and 5, because
the triangles of these pseudoternary systems are not compati-
bility triangles. Both systems contain the primary crystal-
phase field of Hercynite (FeO ? Al2O3), whose composition
is not located in these triangles. It should be noted that the
compositions of the dripped slags in system 5 are slightly
different from the ternary eutectic point of Ano-Geh-Hercyn-
ite or Geh-FeO-Hercynite, as seen in Figure 13. Mullite (3
Al2O3 ? 2SiO2), together with Geh, Hercynite, and Ano or
FeO, was detected in these dripped slags by XRD, indicating
that the dripping compositions would correspond to the qua-
ternary eutectic point of Geh-Ano-Hercynite-Mullite or Geh-
FeO-Hercynite-Mullite, while a precise phase diagram of the
FeO-Geh-Ano-Hercynite-Mullite system is still unknown.
Strictly speaking, systems 2 and 3 are also not a compatibility
triangle, since these sytems contain the primary crystal-
phase field of Olivine (2(Fe, Ca)O ? SiO2), and Olivine is
known to form a wide solid solution with Fayalite (2FeO ?
SiO2), whose composition is not located in these phase dia-
grams. However, in order to estimate the liquid ratio at the
eutectic point in systems 2 and 3, Olivine is assumed to be
a stoichiometric compound as FeO?CaO?SiO2 in the pres-
ent work.
Figure 15 represents a phase-analysis diagram, corres-
ponding to the initial slag composition of sample 201 in
Figure 10, as a typical example of such consideration.
According to Figure 15, this sample consists of 70 pct CS–30
pct Geh below the eutectic temperature (1318 8C), and a
significant amount of liquid is formed just above the eutectic
temperature. This indicates that the sample consists of
approximately 80 pct liquid and 20 pct solid slightly above
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 15—Phase analysis diagram corresponding with the initial slag compo-
sition of No. 201 in Fig. 10.
Fig. 16—Effect of gangue ratio, GR, on the slag holdup on the iron funnel
in FetO-Geh-C2S, FetO-Geh-CS, and FetO-Ano-CS slags at constant FetO
content of 20 and 63 mass pct.
the eutectic point at which dripping occurs and that the slag
remaining on the funnel after dripping should contain some
amount of solid phase of CS. The calculated liquid ratios
for systems 1 through 3 are listed in the last column of Table
I. As can be realized from Table I, the liquid ratios of the
samples are mostly in the range from 60 to 80 pct except
for some slags. Such a large amount of liquid would be
preferentially dripped from the funnel. Since the composition
of sample 204 is very close to the Alkemade line between
Geh and Olivine, this slag has an extremely low liquid-
phase ratio (approximately 3 pct) at 1180 8C (its eutectic
temperature). However, its liquidus temperature is estimated
to be approximately 1210 8C, so that a large amount of
liquid should be formed at a temperature only 30 8C to 40
8C higher than the eutectic point. This consideration based
on the phase-analysis diagram would be helpful in under-
standing the phase composition of the slag during melting
and dripping.
IV. DISCUSSION
A. Comparison of Hold-Up Degree in Five Slag Systems
First to be discussed is the effect of slag composition on
the hold-up behavior of the slag. Figure 16 shows the effect
VOLUME 30B, AUGUST 1999—679

Fig. 17—Effect of gangue ratio, GR, on the slag holdup on the iron funnel
in FetO-C2S-CS and FetO-Geh-Ano slags at constant FetO content at 20
and 63 mass pct.
Fig. 18—Effect of basicity on the slag holdup on the iron funnel. Key as
in Figs. 16 and 17. Open, half-closed, and closed marks are in FetO 5 20,
40, and 63 mass pct, respectively. Numerical values are Al2O3 content in
the initial slag.

of slag composition on the holdup of slag with the iron

funnel, under a fixed FetO content of 20 and 60 to 65 mass
pct, in the FetO-Geh-C2S (system 1), FetO-Geh-CS (system
2), and FetO-Ano-CS (system 4) slags. Since the homoge-
neous liquid region of the FetO-Geh-C2S slag at 1673 K is
limited in the FetO-rich side, the experiment under a fixed
FetO content was conducted only at 63 mass pct of FetO in
this system. With an increasing GR, the Al2O3 content in
each slag system increases, whereas the basicity increases
in FetO-Geh-CS slags but decreases in FetO-Ano-CS slags.
The basicity does not change with a varying GR in the FetO-
Geh-C2S slags. The slag holdup at 63 mass pct of FetO
increases with increasing GR in the FetO-Geh-CS and FetO-
Ano-CS slags, while no measurable effect of GR on the
holdup is observed in the FetO-Geh-C2S slag. At a constant
GR in the same slag systems, the slag holdup is higher at
a lower FetO content. On the other hand, the holdup of the Fig. 19—Effect of Al2O3 content in the initial slag on the slag holdup on
FetO-Ano-CS slag is slightly greater than that of the FetO- the iron funnel. Key as in Figs. 16 and 17. Numerical values are basicity.
Geh-CS slag, at a constant FetO content and GR.
Figure 17 shows the effect of slag composition on holdup
with the iron funnel, at a fixed FetO content of 20 and 60 decreases the slag holdup on the acidic side, but that slag
to 65 mass pct, in the FetO-C2S-CS (system 3) and FetO- holdup reaches the minimum value at a certain basicity
Geh-Ano (system 5) slags. Since the FetO-C2S-CS slag con- around 1 to 1.2 and tends to slightly increase on the basic
tains no Al2O3, only the effect of slag basicity can be inde- side by increasing the basicity. The higher Al2O3 and FetO
pendently investigated in this slag. In the FetO-Geh-Ano contents tend to do so more markedly. Al2O3 significantly
slag, the basicity can be increased under a fixed high-Al2O3 increases the slag holdup when the slag is acidic, while
content (approximately 30 mass pct) by increasing the GR. Al2O3 exhibits very little effect on the slag holdup at a high
The hold-up in FetO-C2S-CS slags slightly increases when basicity and high FetO content. These tendencies are also
CS is exchanged with C2S, as shown in Figure 17. Contrarily, presented in Figures 19 and 20. Figure 19 is the relation
when Ano is exchanged with Geh, the holdup decreases in between the slag holdup and Al2O3 content at FetO 5 20
spite of the increase of the basicity. Similar trends are mass pct as a function of the basicity. It is clearly shown
observed at higher FetO contents but the effect of the GR that Al2O3 makes the slag holdup higher at a lower slag
is much smaller than that at lower FetO contents. From this basicity. Figure 20 represents the relation between the holdup
observation, it is estimated that the extent of the effect of and FetO content as a function of Al2O3 content at three
Al2O3 on the holdup would depend on the slag basicity. levels of basicity (0.8 to 0.9, 1.0 to 1.1, and 1.9). Although
Finally, the effects of the basicity and Al2O3 and FetO the slag holdup does always decrease with increasing FetO
contents on the slag holdup are summarized in Figures 18 content, this effect depends on the Al2O3 content and the
through 20. Figure 18 represents the relation between the basicity. The slag holdup is only a function of FetO content
holdup with an iron funnel and slag basicity as a function at the high basicity of 1.9, while the effect of Al2O3 becomes
of the Al2O3 and FetO contents. At constant FetO and Al2O3 much more significant with a lower basicity and FetO con-
contents, it can be seen from this figure that the basicity tent. For example, when the basicity and FetO content are

680—VOLUME 30B, AUGUST 1999 METALLURGICAL AND MATERIALS TRANSACTIONS B


Fig. 20—Effect of FetO content on the slag holdup on the iron funnel at
various basicities. Numerical values are Al2O3 content in the initial slag.
0.8 and 20 mass pct, respectively, the increase of Al2O3
content from 0 to 30 mass pct results in an approximately
4 times larger slag holdup.
It can be concluded, according to Figures 18 through
20, that Al2O3 increases the holdup of the primary melt,
particularly on the acidic side, and that a high level of Al2O3
in the sinter ore is likely to cause pore blockage of the sinter
by the primary melt in the cohesive zone of the blast furnace.
Some Japanese ironmakers are charging Serpentine into the
iron-ore sinter, expecting the resultant improvements in the
high-temperature strength of the sinter cake, the viscosity,
and the desulfurization ability of the blast-furnace slag by
MgO.[15] However, Serpentine contains a significant amount
of silica, so that the charging of Serpentine makes the basicity
of iron-ore sinter more acidic and amplifies the harmful
effect by Al2O3, unless basicity control is made by charging
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 21—Surface tension and contact angle against the solid iron in FetO-
Geh-CS slag (System 2).
additional CaO together with Serpentine. Therefore, it would
be suggested from the present experimental findings that the
addition of Serpentine into the sinter is not be recommended
for the raw iron ore containing high levels of Al2O3. The
effect of MgO on the slag holdup will be the subject for our
future work.
B. Mechanism of the Hold-Up Phenomenon
It was indicated in the former section that the slag holdup
on the funnel is possibly governed by the slag wettability
against the funnel material. The holdup measured in the
present work is discussed in order to confirm this, based on
the surface tension and contact angle of each slag. There
are some techniques available to measure the surface tension
and contact angel of the liquid slag. The Sessile-drop method
is employed in the present work because this technique is
the most-simple method, and the computer-aided sessile-
drop technique is an established one.[13,14] Since it is gener-
ally difficult to precisely measure the surface tension and
contact angle of a wet slag such as an FetO-containing slag,
the accuracy of the data is not very satisfactory. However,
the authors expect to make a semiquantitative determination
of the hold-up mechanism based on the slag wettability. For
this purpose, the surface tension and contact angle of the
slag remaining on the iron funnel should be known. The
slag compositions for the surface-tension measurement were
adjusted to the observed remaining slag compositions, which
VOLUME 30B, AUGUST 1999—681

Fig. 22—Schematic illustration of the force balance on the liquid slag
suspended by the iron funnel.
are shown in Figures 9 through 12 (systems 1 through 4)
as open circles. In order to avoid the error due to the co-
existing solid phase, slags which have a larger liquid ratio
than 85 pct at 1350 8C were chosen for the surface-tension
measurement. Nevertheless, the samples should contain a
small amount of solid together with liquid at the experimen-
tal temperature.
Some results of the surface-tension and contact-angle
measurements of the slag are presented in Figure 21. Values
of the surface tension of the slag used in the dripping experi-
ment are in the range from 0.4 to 0.5 N/m, which are consis-
tent with the literature data for FetO-CaO-SiO2 and CaO-
SiO2-Al2O3 slags.[16,17,18] The contact angle against the solid
iron shows a large error and is low, in the range of about
10 to 30 deg. This indicates that this slag is likely to wet
solid iron.
Figure 22 illustrates the force balance acted on the sus-
pended liquid on the funnel. It is reasonable to assume that
there are two major forces acting on the liquid; one of them
is a gravity force and the other is the force corresponding
to surface tension. These two forces should balance each
other for the statically suspended liquid. If we can assume
a symmetric shape of the suspended liquid around the verti-
cal axis, solution of this force balance and of the dimension
of the funnel gives a profile of the liquid shape suspended
by the funnel. By integrating this profile around the vertical
axis, the volume of the whole liquid held by the funnel can
be calculated, and the weight of this liquid can be evaluated
682—VOLUME 30B, AUGUST 1999
Fig. 23—Comparison of the observed slag holdup with that estimated from
the surface tension data.
from the available slag density. As a result, we can predict
slag holdup and compare this to the observed hold-up. The
comparison of calculated slag holdup to that observed is
shown in Figure 23. A large scattering of data is observed
due to the aforementioned assumptions for the calculation
and the poor accuracy of wettability estimations. In spite of
such uncertainty, the calculated holdup agrees roughly with
that observed. Therefore, it may be concluded that slag
holdup is governed by the slag wettability of the funnel.
V. CONCLUSIONS
Simulation has been done of the dripping behavior of a
primary melt, which is formed in the iron-ore sinter, through
the pores in the sinter or through reduced iron particles
during reduction in the cohesive or dripping zone of a blast
furnace. The results in the present work can be summarized
as follows.
1. The dripping temperature of slag melt through the hole
of the funnel is much lower than the liquidus temperature
and almost agrees with the corresponding eutectic tem-
perature. The slag melt of eutectic composition does pref-
erentially drip from the funnel.
2. Al2O3 increases the holdup of the slag with the funnel,
and its effect becomes more significant on the more-
acidic side at a constant FetO content and basicity. At
a constant Al2O3 content, slag holdup decreases with
increasing basicity, but it reaches a minimum value at
near-unit basicity and tends to slightly increase with a
further increase of the basicity. However, such effects
of Al2O3 and basicity become insignificant at a high
FetO content.
3. Al2O3 in the ore would lower the temperature at which
primary melt forms in the sinter and increase the holdup
of slag melt in the pore in an iron-ore sinter. It would
result in the harmful effect on the permeability resistance
and indirect reduction of the sinter in the blast furnace.
METALLURGICAL AND MATERIALS TRANSACTIONS B
4. The holdup phenomenon may be explained by slag wetta-
bility against the funnel materials.
ACKNOWLEDGMENTS
The authors are indebted to Mr. Takashige Fujii (formerly
Undergraduate Student, Tohoku University, now with
Sakura-Rubber Co.) and Mr. Atsushi Kumano (Graduate
Student, Tohoku University), for their assistance in the
experiment, and Yoshizawa Lime Industry Co. Ltd. for sup-
plying CaO and MgO funnels. They are also thankful for
financial support by the Grant-in-Aid for Scientific Research
(No. 09650801) from the Ministry of Education, Science,
Sports and Culture of Japan. In addition, the authors extend
their special gratitude for valuable suggestions concerning
the computer program of surface-tension measurement given
by Professor Alan W. Cramb (Carnegie Mellon University,
Pittsburgh, PA) and Professor Itaru Jimbo (formerly with
Carnegie Mellon University, now with Tokai University,
Japan).
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