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Abstract
This paper is centered upon possible eects of the peak temperature attained during sintering upon subsequent reduction of
hematite. To this end, pure hematite compacts were prepared and sintered at various temperatures in the 11001400 C range, and
analysed microscopically before and after reduction. The microstructure undergoes marked changes during high temperature sintering (13701400 C). This change was found to be associated with magnetite formation and subsequent re-oxidation during
cooling. Fine cracks (discontinuities) developing along grain boundaries and the coarse pores and irregular shape of re-oxidised
hematite, associated with the earlier formation of magnetite, inuenced reduction behaviour particularly at 550 C, resulting in
expansion and severe loss of strength. In isothermal reduction tests of pure hematite tablets conducted between 400 and 1200 C,
four types of reduction behaviour were observed. Expansion and strength after reduction were both aected by such changes of the
reduction mechanism. Reduction behaviour was inuenced by both the reduction temperature and nature of the microstructure
prior to reduction.
2003 Published by Elsevier Science Ltd.
Keywords: Reduction; Agglomeration
1. Introduction
In the upper part of the shaft of the blast furnace,
iron-bearing materials such as sinter, pellets and lump
ores exhibit size degradation, which leads to a decrease
in permeability of the blast furnace and aects the stability of operation. After recognition of the importance
of degradation, quality test methods such as ISO 4696
and reduction degradation index (RDI) were established
and used extensively for quality control in industrial
plants. Nakajima et al. (1987) showed that sinter suffered degradation particularly in the temperature range
of 600800 C in the shaft. Furthermore Takada et al.
(1986) showed that degradation of sinter was inuenced
by the reduction conditions as well as by the sinter
quality itself. Degradation increased with the residence
time at 500700 C in the shaft, even though the same
quality of sinter was used.
Two main factors aect the reduction behaviour of
iron-bearing materials in terms of reduction rate and
Corresponding author.
E-mail address: k.higuchi@ta.tudelft.nl (K. Higuchi).
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Some areas of sintering, however, need further elucidation. One of these areas concerns the fundamental sintering behaviour of iron oxide at high temperature
during induration and its inuence upon the subsequent reduction process in the blast furnace. The
present studys objective is to explore the inuence of
sintering conditions on reduction behaviour of iron
oxide in terms of its degradation characteristics under
conditions relating to the upper shaft of the blast
furnace.
TFe
2 55:85
2 71:85
16
55:85
1
TFe
where OB is the oxygen combined with iron oxide (mol);
OR , the oxygen removed during reduction (mol); Fe, the
iron combined with iron oxide (mol), TFe; Total Fe
content before reduction (mass%); FeO, FeO content
before reduction (mass%); DW , the weight loss during
reduction (mass%).
The strength of tablets before and after the reduction
tests was measured by employing a small-scale shatter
strength test. A weight of 300 g was dropped from a
height of 30 cm above the samples twice. The results of
preliminary tests showed that the percentage of particle
size above 1 mm reected the changes in strength of the
tablets well. Therefore the strength of samples was
subsequently dened as the percentage of particle size
over 1 mm after the drops (WA ), against the total weight
before the test (WB ); [Strength of sinter 1 mm; %
WA (gram)/WB (gram) 100]. Measurement error of the
strength test was within 2.4%. Some tablets were analysed by optical microscopy, X-ray diractometry (Philips PW3710) and electron microprobe observations
(JEOL 8800).
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3. Results
3.1. Inuence of sintering conditions
Fig. 2 shows the changes in properties of pure hematite tablets as a function of the sintering temperature.
The average diameter (equivalent circular diameter) of
hematite grains and the total porosity were measured
using image analysis and a screw micrometer, respectively. The magnetite content in sintered tablets was
calculated from weight loss during sintering. Looking at
the results, the changes occurring above 1370 C are
striking. All tablets sintered from 1375 C onward
contained magnetite phase, even after cooling in air.
However, the magnetite content in tablets sintered at
1375 C and 1380 C was quite small (<1%). The porosity ranged from 2% to 16% and had a minimum at a
sintering temperature of 1200 C. The porosity increased
as the sintering temperature was raised, as a result of
crystal grain growth. Above 1390 C, severe cracks were
generated at the surface of the tablets due to volume
changes during the thermal decomposition of hematite
and subsequent re-oxidation of the magnetite formed.
The average diameter of hematite grains increased as the
sintering temperature was increased. Strength increased
up to a sintering temperature of 1350 C, but dropped at
sintering temperatures above this level. In particular
above 1390 C, the strength decreased sharply due to
severe crack development within the structure.
Fig. 3 shows the results of microstructural observation. Observations were made under crossed nicols to
better distinguish the characteristic hematite grain size.
Some of the pores observed in the samples are most
likely due to grain detachment during the polishing
process, which is indicative of weak bonding in the
structure. Microscopic observation of the tablets near
the surface was also carried out closely to see whether
any reactions between iron oxide and air had taken
place.
Above 1385 C, the magnetite formed within the
tablets and microstructure drastically changed in nature.
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Fig. 3. Changes in microstructure of hematite tablets by sintering temperature: (A) crossed nicols, 250; (B) parallel nicols, 500.
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Fig. 4. Inuence of sintering temperature on low temperature reduction behaviour of pure hematite tablets.
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the reduction mechanism of pure hematite tablets, reduction tests without time limit, to complete the transition to magnetite or wustite were also carried out. The
results are also shown in Fig. 5, as paler curves.
There were two temperature ranges to explain reduction behaviour, i.e., low temperature (<630 C)
at which magnetite was stable and high temperature
(>630 C) at which wustite was stable under the prevailing gas conditions. This indicates that changes in the
reduction mechanism observed at 630 C are related to
the change in stable phase.
Basically, expansion increased with the reduction
temperature at both sintering temperatures. However,
expansion exhibited a clear peak at a reduction temperature of 550600 C in the tablets sintered at 1385 C.
Strength and O/Fe changed in a manner corresponding
to the change in expansion. Inuence of the sintering
temperature on reduction behaviour was clearly evident
at low temperature reduction, but became minor at high
temperature reduction. The O/Fe after 30 min following
stabilisation of the expansion was almost the same as the
O/Fe value representing complete transition. However,
in reduction experiments at 630700 C, which is near
the transition temperature between magnetite and wustite, the O/Fe was higher than that of wustite. Even after
a longer period of reduction following stabilisation of
the expansion, the O/Fe did not drop further. Therefore,
the higher O/Fe observed at 630700 C must have been
due to re-oxidation of previously formed, porous wustite
to magnetite during quenching. During reduction of
tablets sintered at 1375 C, expansion after complete
transition increased with the reduction temperature, and
this expansion was much higher than that after 30 min
reduction. This conrms that the low expansion and
high strength observed at low temperatures after only
30 min of reduction was due to the low reduction rate
(high O/Fe) attained in that case. On the other hand,
during reduction of tablets sintered at 1385 C, the expansion after complete transition was similar to that
after 30 min reduction and showed a maximum at a
reduction temperature of 600 C. Tablets fully reduced
to magnetite at 400450 C were extremely weak regardless of the sintering temperature. Therefore, the
relatively high strength observed after 30 min reduction
at 400450 C had to be due to the low reduction
rate (high O/Fe). During reduction of tablets sintered
at 1375 C, the strength increased with the reduction
temperature above 500 C. In addition, the reduction
time required to attain stabilisation of expansion was
quite long at a reduction temperature of 500 C (416
min). This suggests that the reduction mechanisms below and above 500 C are dierent.
The strength of both (30 min and fully reduced)
tablets was relatively high even after complete transition
to wustite, indicating a strengthening mechanism taking
place, e.g. by repair through sintering. This strengthening mechanism is most likely due to a higher mobility of
iron ions in wustite as a result of higher vacancy concentration (von Bogdandy and Engell, 1971).
4. Discussion
4.1. Inuence of sintering temperature on the microstructure
As shown in Figs. 2 and 3, the sintering temperature
strongly inuenced the microstructure, in terms of the
pore structure, grain size and mineralogy of the tablets.
The factors determining the microstructure are as follows:
(1) Physical shrinkage and grain evolution of tablets
during sintering.
(2) Chemical reaction with air or prevailing gas composition at high temperature.
As for shrinkage and grain evolution, the driving force
is minimisation of surface energy. Before sintering, the
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Fig. 6. Microstructures and SEM images of the fracture surface of tablets quenched in water after sintering in air for 4 h.
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Fig. 7. Schematic overview of the inuence of the sintering temperature of pure hematite tablets on microstructural characteristics and on behaviour
during reduction.
Fig. 3A). Most of the magnetite is re-oxidised to hematite during cooling, resulting in further stresses and
crack development. Within the re-oxidised grains the
ne porosity (<1 lm) is retained.
Relating the microstructure before reduction to reduction behaviour, it can be stated that the inuence of
the ne round pores along grain boundaries observed in
material sintered below 1375 C on the initial stage of
reduction is limited, because they are closed and do not
contribute to the diusion of reduction gas. In contrast,
ne cracks (or spaces) along grain boundaries as observed in the structure at 13751385 C are crucial for
the initial reduction rate, since they are particularly located in the surface region of tablets. Once reduction has
been initiated in the surface zone, it can proceed in a
self-promoting fashion due to expansion of formed
magnetite. Coarse pore formation and the irregular
shape of re-oxidised hematite as observed above sintering temperatures of 1385 C, also contribute to the
reduction rate as a result of the increased surface area
available for reduction. Reduction was found to proceed rapidly above a sintering temperature of 1380 C,
which tends to support the proposed sintering mechanism.
In the present study, a small amount of magnetite was
already observed to be formed at 1375 C in air. The
formation reaction of magnetite is expressed in Eq. (2).
DG (standard Gibbs energy change) for this reaction
was derived from thermodynamic data (Elliot and Gleiser, 1960; Barin and Knacke, 1973; Kubaschewski and
Alcock, 1979; Turkdogan, 1980). Using Eq. (3), the
transition temperature between hematite and magnetite;
TH>M in air PO2 0:21 105 Pa) can be calculated.
3Fe2 O3 s 2Fe3 O4 s 1=2O2 g
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473
Fig. 8. Microstructure of tablets after reduction (H; Hematite, M; Magnetite, W; Wustite, Re-H /Re-M; Re-oxidised hematite/magnetite during
quenching).
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475
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5. Conclusions
The main conclusions based on the present work have
been summarised in schematic overviews in Fig. 7,
concerning the eect of peak induration temperature,
and in Fig. 11, comparing the eects of low- to high
temperature reduction in its interaction with the microstructure derived from induration. More general
conclusions are the following:
1. The nature of the microstructure of material coming
out of the induration stage is the determining factor
for reduction geometry and rate, which in turn aect
internal stress development, expansion of the material and its dynamic strength.
2. Peak induration conditions from 1380 to 1385 C onward in air, and starting at lower temperature levels
under lower oxygen conditions, generate transition
from hematite to magnetite from the surface inward,
from occasional, individual crystallite grains at the
low end of the temperature range to massive transformation at 1400 C.
3. Transition of hematite grains to magnetite during induration, followed by re-oxidation to hematite upon
cooling, results in increasingly irregular grain shape
and increasing size coupled with buildup of stresses.
Consequently, ne cracking and disengagement of
grains takes place particularly in the surface region,
in addition to coarse pore formation. The result is a
relatively weak, open structure amenable to rapid reduction and breakdown.
4. Sensitivity to weakening of the iron-bearing material
during reduction varies with the conditions employed. A high reduction rate yields lower strength
after reduction from hematite to magnetite, and from
magnetite to wustite. At low reduction temperature
(<500 C), the slow reduction rate limits the weakening process, while at higher temperatures (>630 C)
weakening is also limited due to re-strengthening of
the wustite structure, most likely through sintering.
At moderately low temperatures ( 500630 C) the
reduction rate is high, without noticeable repair,
and signicant weakening results, particularly if an
open structure is involved.
5. Very ne closed porosity (<2 lm) derived from recrystallisation during sintering tends to transfer to
the hematite grain boundaries, but appears to be of
limited, if any, signicance to the subsequent reduction rate.
Acknowledgement
The authors wish to thank Nippon Steel Corporation
for their nancial support.
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