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Minerals Engineering 16 (2003) 463477

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Inuence of sintering conditions on the reduction behaviour


of pure hematite compacts
K. Higuchi *, R.H. Heerema
Department of Applied Earth Sciences, Delft University of Technology, Mijinbouwstraat 120, 2628RX Delft, The Netherlands
Received 13 July 2002; accepted 23 August 2002

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).

size degradation, i.e., the nature of the materials and the


reduction conditions. Macroscopically, the size and
shape of the individual agglomerate particles play a role
(Kang et al., 1998a,b), and microscopically, the pore
structure, grain size and mineralogy. The microstructure
of the agglomerates is inuenced by the starting materials, shaping methods and sintering conditions, especially at high temperature. With regard to the reduction
conditions, much work has been published, using various materials for testing. Natural or synthesised single
crystals of hematite were used in some investigations to
clarify the reduction mechanisms (Edstr
om, 1953;
Swann and Tighe, 1977; Hayes and Grieveson, 1981; EtTabirou et al., 1988). In other work, nely ground
natural ore (Hayes and Grieveson, 1981), plant pellets
nal and Bradshaw, 1983), or synthesised hematite
(U
compacts were used. Even in the case of synthesised
hematite compacts, the starting materials and sample
preparation methods were dierent from investigation
to investigation. As a result of these dierences, the
grain diameter of hematite grains and the pore structure
within the samples must dier, and hence strongly aect
the reduction characteristics. Nevertheless, information
on the inuence of the microstructure of hematite

0892-6875/03/$ - see front matter 2003 Published by Elsevier Science Ltd.


doi:10.1016/S0892-6875(02)00180-2

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K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

compacts or agglomerates on their reduction behaviour


is limited (El-Geassy and Nasr, 1990).
In the industrial sintering process of iron ores, the
temperature prole consists of three stages, i.e., heating,
holding for a few minutes at the maximum temperature
and cooling down. The raw materials are rst heated by
combustion of the coke breeze mixed in. The downward
airow and the presence of a water condensation zone
result in a high heating rate of the raw materials, in the
range of 6001000 C/min. The maximum temperature
of the sinter bed ranges from 1200 to 1350 C. It depends on the content of coke breeze as a source of heat,
and on limestone and water as heat absorbers. Bed
height also has an inuence on the maximum temperature by way of accumulation of heat. Afterwards, the
raw materials are cooled by an air stream, the cooling
rate depending on the air ow rate. In the case of constant suction sintering, it is inuenced by the permeability of the sintering bed as well. Hida et al. (1984) and
Hsieh and Whiteman (1989a,b) demonstrated the large
inuence of the prevailing atmosphere on the formation
of mineral phases. They concluded that the industrial
sintering process takes place in a slightly reducing atmosphere in which the partial pressure of oxygen (PO2 ) is
101 102 Pa. Under these moderately low PO2 conditions, the equilibrium temperature between hematite
and magnetite ranges between 900 and 1100 C (Turkdogan, 1980). Therefore, hematite, a major constituent
of iron ore sinter, is easily decomposed to magnetite
during heating, and most of this magnetite is readily reoxidised to hematite during subsequent cooling.

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.

2. Materials and methods


Reagent Fe2 O3 (purity; >99%, grain diameter; <5
lm) was used as a starting material. After mixing and
adding 8% water, the ne mixture was shaped into a
tablet. Tablets were made by using a steel mould under
a pressure of 86.8 MPa. The green tablets which had a
diameter of 12 mm, a height of approximately 3 mm and
a weight of 1 g (initial porosity was 28%) were sintered
for 4 h at several temperatures (10001400 C) in a
mue furnace under an air stream of 2 l/min. After
sintering, tablets were cooled in the furnace under the air
stream. The cooling rate was 36 C/min.
Reduction tests were carried out in a dilatometer as
shown in Fig. 1, in which the vertical expansion of a
sample was measured during reduction (Husslage et al.,
1999). In the present study, all tests were performed
under a constant reduction potential, i.e., temperature
and gas composition, in order to clarify the nature of

Fig. 1. Schematic diagram of dilatometer.

K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

hematite samples exposed to industrial conditions. The


reduction gas was a mixture of CO, CO2 and N2 . Gas
composition was set at CO 22:5%, CO2 27:5% and
N2 50% so that it would simulate the actual top gas
composition prevailing in the blast furnace. As a result,
Fe3 O4 is stable below 630 C and FeO is stable above
this temperature (Darken and Gurry, 1945). Total gas
ow was maintained at 2.0 l/min. The supercial gas
velocity at standard state was 30 cm/s and suciently
high to prevent reduction gas starvation in the gas phase
(Yamaoka et al., 1982). The sample was rst heated to
the desired temperature in N2 . After stabilisation of
both the temperature and its corresponding thermal
expansion, the reduction gas was led into the chamber.
Reduction time was set mainly for a period of 30 min.
Following reduction, the sample was quenched in water
to x the existing microstructure and limit back-oxidation. Reduction temperature was usually xed at 550 C,
but some tests were carried out in the temperature range
of 4001200 C.
Before and after reduction, the dimensions and
the weight of a sample were measured to determine the
volumetric expansion and the degree of reduction. The
latter was estimated using O/Fe as the mole ratio after
reduction, in terms of the mole ratio derived from the
weight change during reduction by the following equation:
OB  OR
O=Fe in moles
Fe


3
1
DW
 FeO 

 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).

465

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.

Fig. 2. Changes in properties of pure hematite tablets as a function of


sintering temperature.

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K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

Fig. 3. Changes in microstructure of hematite tablets by sintering temperature: (A) crossed nicols, 250; (B) parallel nicols, 500.

As for grain size and shape, hematite grain size was


extremely ne at less than 5 lm below 1100 C due to
the low diusion rate at those temperatures. Above
1200 C, spherical hematite grains were apparent. Their
size increased as the sintering temperature was raised,
from approximately 10 lm at 1200 C to 28 lm at

1380 C. At 1385 C, many small pores were observed


inside the hematite grains and the shape of hematite
grains had become irregular. Above 1390 C, hematite
grains were large (70110 lm) and the shape of the
grains was even more irregular. Three types of pores and
two types of cracks were observed:

K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

(1) Fine pores of less than 2 lm were observed within


crystallite grains in all samples. However, these ne
pores tended to be located along grain boundaries above
1200 C.
(2) Large pores (about 20 lm) were observed within
grains at 13901400 C.
(3) Fine pores of less than 1 lm diameter, which were
located near the interface between hematite and magnetite, were observed at 13851400 C.
(4) Fine cracks along grain boundaries were observed
near the surface at 13001350 C. However, their
number was small. No magnetite formation was observed at those temperatures. Therefore these ne cracks
were most likely due to thermal shock during cooling.
Fine cracks along grain boundaries increased in number
as the sintering temperature was raised up to 1380 C.
Detachment of grains during polishing was enhanced by
those ne cracks along the grain boundaries.
(5) Fine intra-particle cracks were observed at 1385
1400 C. Near the cracks magnetite phase was formed.
Magnetite was formed not just at the surface, but also
inside the tablet in the surface zone. Hematite then
formed once again around the magnetite phases upon
cooling.
(2), (3) and (5) were observed only at high temperatures, accompanied by the formation of magnetite.
Therefore, it became clear that development of these
microstructures was associated with the formation of
magnetite and subsequent re-oxidation to hematite.
Fig. 4 shows the relationship between reduction behaviour (vertical expansion, strength and degree of reduction) and the sintering temperature of pure hematite
tablets. All reduction experiments were carried out at
550 C for 30 min. Expansion showed a maximum in
tablets sintered at 1385 C. Strength after reduction
dropped in correspondence with the expansion. The
degree of reduction was small up to a sintering temperature of 1350 C. However, above 1350 C, the degree of reduction increased with higher sintering
temperatures and reached almost complete transition to
magnetite in tablets that had been sintered at temperature levels of 1385 C and above.
To clarify the reduction mechanism of pure hematite
tablets, long duration reduction tests were performed
until all the hematite had transformed to magnetite. The
reduction conditions were based on the following standard condition (gas composition: CO 22:5%, CO2
27:5%, N2 50%, reduction temperature: 550 C). 30
min after stabilisation of the expansion curve during
reduction, the sample was quenched in water to x the
mineralogy at the reduction temperature.
The results of the inuence of the original sintering
temperature following complete transition from hematite to magnetite are shown in Fig. 4 as well, the corresponding curves indicated by triangles. Tablets sintered
below 1375 C required much longer reduction time to

467

Fig. 4. Inuence of sintering temperature on low temperature reduction behaviour of pure hematite tablets.

reach complete transition from hematite to magnetite


than tablets sintered above 1380 C. However, ultimately the tablets sintered at 1375 C showed a large
expansion. Therefore, the reason behind the limited
expansion below 1375 C in the 30 min tests must be the
relatively low reduction rate due to a compact structure.
3.2. Inuence of the reduction temperature
Isothermal reduction tests of pure hematite tablets
sintered at dierent temperatures were performed at 400
1200 C at a constant gas composition. Tablets, which
had previously shown clearly dierent indurated characteristics and dierent reduction behaviour at 550 C
(Fig. 4), were selected (sintered at 1375 and 1385 C,
respectively, in air for 4 h). Fig. 5 shows the inuence of
the reduction temperature. All reduction experiments
were performed under the following standard conditions,
except the reduction temperature (reduction time: 30
min, gas composition: CO 22:5%, CO2 27:5%, N2
50%). Wustite composition (O/Fe) in equilibrium with
the prevailing COCO2 N2 gas was calculated from literature data (von Bogdandy and Engell, 1971). To clarify

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K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

Fig. 5. Inuence of reduction temperature on the reduction behaviour


of pure hematite tablets.

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

K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

green tablets had a porosity of 28% and the crystallite


grain size of hematite was less than 5 lm. Most of the
porosity is represented by space between hematite particles (open pores), and the remainder is closed porosity
inside those particles. Open pores gradually diuse to the
surface of tablets and closed pores tend to diuse to the
interface between grains during sintering to minimise
the surface energy. This results in shrinkage of the
tablet and a decrease in porosity. Despite these trends,
porosity is not completely driven out of the tablets and
remains apparent after sintering. Growth of grains also
takes place at the contact points by diusion in the solid
state. Larger grains grow by incorporating contacting
smaller grains to decrease their total surface area.
The chemical reaction during sintering takes place
between iron oxides and oxygen and is represented by
decomposition of hematite and re-oxidation of formed
magnetite Eq. (2).
3Fe2 O3 s 2Fe3 O4 s 1=2O2 g

If this reaction takes place during sintering, the pore


structure of the tablets must be strongly aected because the lattice structure of both minerals is quite different, and may result in stress development within
hematite grains. It has been reported in the literature
that c-Fe2 O3 (maghemite), a metastable phase as opposed to a-Fe2 O3 (Shultz and McCarthy, 1988), is initially formed during oxidation of magnetite (Edstr
om,
1953; David and Welch, 1956; Ball et al., 1973;
Basantsev, 1976).
To clarify the evolution process in the microstructure
of tablets, water-quenched samples were analysed.
Green tablets were sintered at various temperatures,
from 1350 to 1400 C, in air for 4 h and subsequently
quenched in water to freeze the mineralogy existing at
high temperature. To determine both the mineralogy
and possible strain development in hematite grains, Xray diraction analysis was also carried out. The quenched samples were crushed to less than 200 mesh and
mixed with 33 mass% reagent Si powder. Relative intensities of the hematite(1 0 4) and magnetite(2 2 0) peaks
against the standard Si peak were quantied from results of the X-ray diraction analysis.
Fig. 6 shows the polished sections and SEM images of
a fracture surface of water-quenched tablets sintered at
1350, 1375, 1380 and 1400 C, respectively. The hematite to magnetite proportions in the tablets are indicated
in Fig. 6.
(a) At a sintering temperature of 1350 C, no magnetite formation took place. The microstructure was
almost the same as for the normal sample cooled in air,
which is shown in Fig. 3. Magnetite was formed from
1375 C onwards, as can been seen in the water-quenched samples in Fig. 6. After normal cooling in air, there
was no magnetite phase left at 1375 C, as shown in

469

Fig. 3. The dierence in magnetite content before and


after cooling indicates that re-oxidation of the formed
magnetite near the surface took place during cooling in
air. In the quenched sample, re-oxidised hematite was
also observed at the surface, which must have been
formed during the water-quenching itself. The amount
of magnetite increased with the original sintering temperature. At 1400 C, hematite was completely decomposed to magnetite prior to cooling. At this temperature,
11 mass% of magnetite was still found to be present after
normal cooling in air, as shown in Fig. 2. Most of the
hematite found in the tablets following normal cooling
in air must therefore have been re-oxidised. The grain
shape was changed from a regular shape to an elongate,
continuous shape at 1400 C. It is clear that a signicant
structure change must have already taken place during
the decomposition of hematite, prior to cooling, at this
temperature. Hematite was subsequently formed around
these continuous grains and large pores, implying that
this happened during water-quenching. Re-oxidation of
magnetite must have taken place briey, but at a high
rate. With regard to the lower sintering temperatures, all
of the formed magnetite was re-oxidised below 1380 C
during air cooling, while above 1385 C, some of the
formed magnetite remained even after cooling.
(b) From the observation of SEM images of the
fracture surface, signicant dierences were not observed at 13501380 C. However, at 1400 C the image
of the fracture surface changed. At sintering temperatures of 13501380 C, fracture mostly took place along
the grain boundaries of hematite grains. No large pore
was observed and the structure of the surface was
compact. Therefore the many pores seen in polished
cross-sectional images as shown in Fig. 3 must have
been caused during the polishing process due to plucking-out eects. Many ne, rounded pores (about 2 lm
diameter) were observed along the hematite grain
boundaries. Some fracture surfaces also showed intraparticle fracture. Such fracture surfaces contained only a
small amount of ne pores. At a sintering temperature
of 1400 C, a fracture pattern could not be deduced
conclusively from the observations because the fracture
surface was complex. The originally compact structure
of roundish grains disappeared and a continuous
structure (of large magnetite grains) formed, enclosing
pores of the order of 10 lm diameter.
(c) X-ray diraction analysis showed that the minerals present were hematite (a-Fe2 O3 ) and magnetite, and
the presence of maghemite (c-Fe2 O3 ) was not detected in
any of the water-quenched samples. The d-spacing for
hematite in the tablets sintered between 1350 and
1385 C was virtually constant. In contrast, the d-spacing
for hematite in the tablet sintered at 1400 C showed a
clear shift, which is due to the partial re-oxidation of
magnetite during quenching. Considering that hematite
was not a major constituent mineral at 1400 C, it can be

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K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

Fig. 6. Microstructures and SEM images of the fracture surface of tablets quenched in water after sintering in air for 4 h.

deduced that there could not have been a signicant


strain within hematite grains in the case of tablets sintered below 1380 C.

The conclusion is that neither the formation of


maghemite, nor strain within hematite grains can be the
reason behind the observed dierences in reduction

K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

471

Fig. 7. Schematic overview of the inuence of the sintering temperature of pure hematite tablets on microstructural characteristics and on behaviour
during reduction.

behaviour. Therefore, the unusually large expansion


during reduction following sintering temperatures of
13801385 C must be associated with the formation of
magnetite in the sintering stage.
From microstructural analysis, the mechanisms
occurring during sintering, i.e., the evolution of microstructures of pure hematite, are proposed and summarised in Fig. 7. Below 1200 C, the grain growth rate
is low, resulting a small grain size of less than 5 lm.
Fine pores from space among initial particles, and
original ne closed pores within particles are distributed
homogeneously. At 12001375 C, further grain growth
proceeds and the crystallite grain size reaches approximately 30 lm. Many ne pores (<2 lm) are trapped,
mainly at grain boundaries of the hematite. Some ne
pores remain within the interior of the grains. Above
1300 C a small number of cracks are formed along
grain boundaries due to thermal shock during cooling.
At 13751385 C, hematite grains near the surface of the
tablets decompose to magnetite. Most of them are reoxidised to hematite again during cooling. Due to the
formation and subsequent re-oxidation of magnetite,
stress develops due to volume increases and results in
creation of a small amount of space between re-oxidised
hematite and primary hematite grains. Above 1385 C a
more marked microstructural change takes place. Most
hematite grains decompose to magnetite, while at the
same time fairly strong grain growth takes place, attaining sizes in the order of 110 lm. Formation of large,
irregularly shaped magnetite grains results in development of coarse pores between the latter and surrounding
hematite grains, and in generation of ne pores (<1 lm)
within the magnetite grains due to volume changes.
During this process, some intra-particle cracks may be
generated due to stress within the magnetite grains (see

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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K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

DG 249; 450  140:67  T J


Kubaschewski and Alcock; 1979
DG 237; 990  137:26  T J Turkdogan; 1980
!
1=2
a2Fe3O4  PO2
DG RT  ln
a3Fe2O3
3
12  RT  ln PO2
Calculation results using thermodynamic data, for TH>M
in air were 1403 C (Elliot and Gleiser, 1960), 1440 C
(Barin and Knacke, 1973), 1422 C (Kubaschewski and
Alcock, 1979) and 1383 C (Turkdogan, 1980). The
disparity between these results was rather large at 57 C.
Muan (1955) and Chaigneau (1994) directly measured
TH>M in air, and found this to be at 1390 and 1380 C,
respectively. Their results show that the measured
transition temperature tends to be lower than calculated
from thermodynamic data. However, in the present
study a small amount of magnetite was observed in the
surface region even at a sintering temperature as low as
1375 C. Possible sources of deviation from the literature data might be (1) inhomogeneous temperature
distribution within the mue furnace, (2) PO2 being
slightly lower than 0:21  105 Pa due to oxygen consumption within the mue furnace, (3) the inuence of
impurities within the chemical reagent grade materials.
The chemical reagent grade hematite used in present
study contained a maximum impurity level of 1%.
Through sensitive TGA analysis of 99% and 99.999%
pure hematite in air, TH>M in air was found to be at 1386
and 1389 C, respectively. Although factor (2) would
appear the most likely source of the dierence, the discrepancy was not further pursued since under commercial sintering conditions a low PO2 will always be
prevalent and hence lower-temperature formation of
magnetite is to be expected.
4.2. Inuence of reduction conditions on the microstructure
Fig. 8 shows the microstructures of tablets after reduction at dierent temperatures. At all reduction temperatures, reduction progressed in a topochemical
fashion. At reduction temperatures of 450 and 550 C,
magnetite was formed at the surface of the tablets. At
450 C, reduction progressed mainly along the grain
boundaries due to a slow chemical reaction rate. It resulted in unreduced hematite remaining inside the topochemically reducing grains. Grains did not impinge
on each other and the bulk structure was quite loose. In
contrast, at 550 C a clear reaction front appeared. Near
the reaction front, some incompletely reduced hematite
grains surrounded by formed magnetite were visible.
The magnetite layer appeared dense, with grains growing together and with poorly dened grain boundaries as

indicated in Fig. 8. On the other hand, the magnetite


layer near the reaction front still showed a loose structure and there were spaces between grains. At 800 C, a
wustite layer developed on the outside of the magnetite
zone and the reaction front became more clear-cut topochemical. The layer thickness of both magnetite and
wustite increased with the reduction temperature. No
unreduced hematite grains were found remaining in the
magnetite zone. In the tablets sintered at 1375 C, a
porous form of wustite developed, with the pores more
or less perpendicularly facing the reduction front. A
small amount of re-oxidised hematite at the surface of
the tablet must have developed upon removal from the
furnace and during water quenching. The wustite
formed following a sintering temperature of 1385 C
showed a dierent structure after reduction, in comparison with the one sintered at 1375 C. This was most
likely due to the irregular shape of the initial hematite
before reduction as shown in Fig. 3. The magnetite zone
in the interior (near the reaction front) had a loose
structure, with spaces between the grains. At 1000 C,
reduction was almost complete and most of the constituent phase was wustite. This wustite contained less
pores, while the space between grains increased. At
1200 C, the wustite was sintered and showed a continuous phase containing porosity.
Considering low temperature reduction of hematite,
two possible mechanisms can be postulated as follows:
(a) If the formed magnetite layer is dense, CO gas reacts
at the magnetite surface to form iron ions (1); these
ions diuse through the magnetite layer (2); hematite and iron ions react to form magnetite at the interface between hematite and magnetite (3A).
(b) If the formed magnetite layer is porous, CO gas can
readily diuse through the pores and directly react
with hematite at the interface (3B).
4CO Fe3 O4 ! 3Fe2 2e 4CO2 (step 1)
Diusion of Fe2 through the magnetite layer
(step 2)
4Fe2 O3 Fe2 2e ! 3Fe3 O4 (step 3A)
CO 3Fe2 O3 ! 2Fe3 O4 CO2 (step 3B)
Many past investigations reported that the morphology of magnetite formed during transition from
hematite was inuenced by the reduction conditions.
Bradshaw and Matyas (1976) investigated the reduction
of plant pellets using a COCO2 gas mixture, and found
that porous magnetite formed below 800 C and
lamellar magnetite above this temperature. Swann and
Tighe (1977) distinguished three types of magnetite reduced from hematite, i.e., porous, plate or transitional
types, respectively. They reported that the reduction
temperature determined the morphologies of magnetite.
On the other hand, other authors showed that the reduction atmosphere such as partial pressure of oxygen

K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

473

Fig. 8. Microstructure of tablets after reduction (H; Hematite, M; Magnetite, W; Wustite, Re-H /Re-M; Re-oxidised hematite/magnetite during
quenching).

nal and Brad(Hayes and Grieveson, 1981) or CO (U


shaw, 1983) had an inuence upon the morphologies of
magnetite as well. Et-Tabirou et al. (1988) observed
fracturing by open cracks during low temperature reduction of a hematite single crystal. Cracking was also
reported in newly formed magnetite after reduction
(Brill-Edwards et al., 1965; Bradshaw and Matyas,
1976). However, these cracks apparently did not act as a
gas diusion route, according to microstructural obser-

vation. Apparently, the reduction rate is controlled by


chemical reaction at the interface between hematite and
magnetite, and reduction proceeds topochemically as
opposed to following cracks. In the present study, porous magnetite was formed and the reduction proceeded
in topochemical fashion during low temperature reduction. The observations were in line with literature data
below 550 C. Therefore, it can be concluded that
reduction at low temperature proceeds according to

474

K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

reduction mechanism (b). However, in the present study


it was also clearly shown that the microstructures of
tablets reduced at 450 and 550 C were dierent from
each other. The transition temperature of the microstructure corresponded to the observations of Et-Tabirou et al. (1988). Furthermore, it was found that the
morphology of the formed magnetite was inuenced by
the sintering temperature, when a reduction temperature
of 550 C was employed. As shown in Fig. 8, the formed
magnetite corresponding to a sintering temperature of
1385 C was cracked, while magnetite formed following
sintering at 1375 C was not. This dierence might be
due to the reduction rate, as a result of a dierent initial
pore structure as mentioned before. In the present study,
porous magnetite was formed even at a reduction temperature of 800 C. This result was dierent from past
observations (Bradshaw and Matyas, 1976; Swann and
nal and Bradshaw, 1983). The disparity is
Tighe, 1977; U
most likely due to a dierent gas composition. In the
present study the stable phase under the prevailing
conditions at 800 C was wustite, and hence the reduction mechanism was dierent from those reported in the
literature.
With regard to higher temperature (>630 C), the
reduction of hematite to wustite can be expressed as
follows:
CO Fe1y O ! 1  y Fe2 2e CO2 (step 1)
Diusion of Fe2 through the wustite layer (step 2)
Fe3 O4 1  4yFe2 2e ! 4Fe1y O (step 3A)
1  4yCO 1  yFe3 O4 !
3Fe1y O 1  4yCO2 (step 3B)
Diusion of Fe2 through the magnetite layer (step 4)
4Fe2 O3 Fe2 2e ! 3Fe3 O4 (step 5A)
CO 3Fe2 O3 ! 2Fe3 O4 CO2 (step 5B)
where y is mole fraction of vacancies in wustite.
y 0:082 at the equilibrium between wustite and gas,
y 0:104 at the equilibrium between wustite and magnetite at 800 C. If the product magnetite and wustite
layers would be suciently dense, no gas diusion could
take place, and reduction would proceed according to
route 1 ! 2 ! 3A ! 4 ! 5A. The diusion rate of Fe
ions in magnetite (4) is quite slow compared with that in
wustite (von Bogdandy and Engell, 1971), and therefore
the former controls the reduction rate at high temperature. In this reduction mechanism, the layer thickness of
magnetite during reduction is small and 102 times that
of wustite (von Bogdandy and Engell, 1971). If only the
wustite product layer is porous, CO gas can readily
diuse to the reaction surface on the magnetite layer.
Reduction then proceeds according to 3B ! 4 ! 5A. In
this reduction mechanism, the magnetite layer is relatively thin because the controlling step of the reduction
is diusion of Fe ions through the magnetite layer. If
both the magnetite and wustite product layers are po-

rous, reduction gas can react directly at the hematite and


magnetite surfaces. Reduction then follows 3B 5B. In
the case where the chemical reaction rate of 3B (magnetite to wustite) is lower than that of 5B (hematite to
magnetite), the hematite layer disappears during reduction and from then on, only reduction of magnetite to
wustite takes place. In the case where the chemical reaction rate of 3B (magnetite to wustite) is larger than
that of 5B (hematite to magnetite), the hematite layer
remains present until end of reduction. In the present
study, the layer thickness of magnetite at 800 C was
large (Fig. 8). Therefore, reduction proceeds through
direct contact of gas with the hematite/magnetite surface. It was also evident from the results that the transition to wustite was still not complete even after
stabilisation of the expansion, and hence the reduction
rate of hematite to magnetite was suciently high to
maintain a thick magnetite layer. Only during the nal
stages of reduction did completion of the transition
from magnetite to wustite take place.
Fig. 9 shows the relationship between reduction behaviour and the degree of reduction (O/Fe) of tablets
sintered at several temperatures. Standard reduction
conditions, as dened earlier, were used. Therefore, the
stable phase is magnetite during reduction at 450 and
550 C (O=Fe 1:33), and wustite during reduction at
800 C (O=Fe 1:09). It is evident that the properties
measured change with the reduction temperature. In
particular, the fact that strength after reduction decreases with the degree of reduction at 800 C tends to
support the mechanism proposed for high temperature

Fig. 9. Relationship between reduction behaviour and degree of reduction.

K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

reduction. If only magnetite would have formed during


the rst stage of reduction, the strength after reduction
would have been decreased by the same level as during
reduction at 550 C. Looking more specically at
550 C, two reduction mechanisms can be identied.
Evidently, the reduction behaviour changed depending
on the original sintering temperature at this reduction
temperature level. Since one of reasons might be the
dierence in reduction rate, a number of tests were
performed to bear out this inuence. To change the reduction rate, the partial pressure of CO (PCO ) was varied
by changing the proportion of N2 in the gas mix at a
constant CO2 /(CO CO2 ) ratio ( 55%). Reduction
temperature was 550 C. Pure hematite tablets sintered
between 1350 and 1385 C were tested. Fig. 10 shows the
relationship between reduction behaviour and PCO . Expansion increased slightly and the strength decreased
with the reduction rate (PCO ). A similar inuence of reduction rate on expansion has been reported elsewhere
(Edstr
om, 1953). Hence, the spread in reduction properties at 550 C depending on the sintering temperature
was most likely due to the reduction rate. If the tablets
contain many pores or cracks prior to reduction, the
reduction rate is high, resulting in high expansion and
decrease of strength (e.g., in tablets sintered at 1380 and
1385 C). If the tablets are more dense, the reduction
rate is quite low, resulting in low expansion and high
strength even after complete transition to magnetite
(tablets sintered at 1375 C).
Fig. 11 shows a summary of the proposed reduction
mechanisms. The reduction mechanism changes with the

Fig. 10. Inuence of the reduction rate (represented by PCO on the


reduction behaviour of pure hematite tablets).

475

Fig. 11. Schematic classication of reduction behaviour mechanisms


(magnication, 250 for A, B1 and B2, 120 for C, arrows indicate
the direction of reduction).

reduction temperature. Furthermore, during reduction


to magnetite at 500630 C, the reduction mechanism
was also aected by the sintering temperature.
Mechanism A: During low-temperature reduction
to magnetite (400500 C), reduction gas diuses into
and inside tablets via pores and cracks along the grain
boundaries. However, reduction into the interior of
individual grains is limited by the low chemical reaction rate at the interface between hematite and magnetite. Porous magnetite surrounding hematite cores
in the individual grains causes a loose structure of
the tablets, which results in low strength. Stress developing in the surrounding magnetite, however, is
distributed homogeneously, which results in low expansion.
Mechanism B: During moderately low-temperature
reduction to magnetite (500630 C), two types of reduction mechanism are identied. Chemical reaction
rate is increased by the increase in reduction temperature, resulting in formation of a well-dened topochemical layer of magnetite from the outside inward.
The straightened reduction front causes anisotropic
stress, resulting in increased expansion. However, in the
case of reduction of dense tablets, reduction proceeds
only by chemical reaction between hematite and magnetite. This reduction is rather slow. Therefore, the
formed magnetite is annealed and the stress is eased,
which results in a moderate level of expansion and
relatively high strength (Mechanism B1). In the case

476

K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

of reduction of more porous tablets, pores and cracks


along the grain boundaries promote reduction. Therefore, the reduction rate is high, which results in
high expansion levels and low strength (Mechanism
B2).
Mechanism C: During high temperature reduction to
wustite (6301200 C), the high chemical reaction rate
results in concentric topochemical layers of magnetite
and wustite. Reduction rate is controlled by the chemical reaction rate. Because both the formed magnetite
and wustite layers are porous, reduction gases readily
diuse into these regions. The thus formed, more or less
straight reaction front causes anisotropic stress, which
results in high expansion.

4.3. Relevance for plant operation


Comparing the materials used in the present study
with plant sinter, two major dierences should be noted.
Generally, basic plant sinter contains 5060% bonding
phase such as SFCA (silico-ferrite of calcium and aluminium) (Wang et al., 1998) and silicate slag, and about
40% porosity. Nevertheless, trials have been carried out
to increase the iron content in sinter in order to decrease
the energy consumption, which in turn, results in an
increase in hematite phase (Yamaguchi et al., 1999). In
addition, the microstructure of plant sinter is heterogeneous and large, dense unreacted grains of iron ore remain in the structure. If such relict hematite undergoes
high temperature sintering under relatively low PO2
conditions, formation of magnetite and subsequent reoxidation can take place, which might result in high size
degradation during subsequent reduction. To prevent
size degradation, avoiding high sintering temperature
levels on the strand would be eective in avoiding the
formation of magnetite which would then re-oxidise
during cooling, etc. With regard to reduction conditions,
these are not isothermal in plant blast furnace operation. The reduction temperature of materials increases
gradually following their charging into the furnace. At
the same time the reduction gas composition gradually
shifts to higher partial pressure of CO. Nevertheless, the
results of isothermal reduction at low temperatures are
important, because once material experiences size degradation at low temperature, it is dicult to recover the
strength at higher temperatures because of the low solid
state re-sintering rate (Chaigneau et al., 1997). In the
present study, four types of reduction behaviour were
observed. In particular, reduction under conditions at
which magnetite is stable showed severe size degradation. Hence, if the reduction time under the conditions
where magnetite is stable is kept short, the strength
should be maintained during further reduction at higher
reduction temperature and less degradation would be
the result.

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.

K. Higuchi, R.H. Heerema / Minerals Engineering 16 (2003) 463477

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