ISIJ International, Vol.

59 (2019),
ISIJ International,
No. 2 Vol. 59 (2019), No. 2, pp. 227–234

Effect of Silica on Reduction Behaviors of Hematite-carbon

Composite Compact at 1 223–1 373 K

Zhikai LIANG, Lingyun YI, Zhucheng HUANG,* Biao LU, Conglin DAN and Ronghai ZHONG

School of Minerals Processing & Bioengineering, Central South University, Changsha, Hunan, 410083 China.
(Received on September 11, 2018; accepted on October 22, 2018; J-STAGE Advance published date:
December 13, 2018)

The influence of compositional changes in the SiO2–Fe2O3 binary oxide system on the reduction behav-
ior of carbon-bearing compact was investigated at 1 223–1 373 K. Density functional theory (DFT) calcula-
tions were employed to investigate the adsorption behaviors of O–Si–O on various FeO surfaces in order
to explore the mechanism of the conversion of FeO to Fe–Si–O phase. Chemical analysis, SEM-EDX, and
XRD were carried to characterize the conversion mechanisms. According to experimental results, silica
causes the decrease of the metallization ratio by hindering the reduction of FeO to Fe and facilitating the
reaction of FeO to Fe–Si–O phases. The size of metallic iron granules diminishes gradually and the bound-
ary between the iron phase and the slag phase becomes less obvious with increasing silica content, which
greatly increases the contact probability of SiO2/liquid phases and FeO. For the three adsorption sites, the
adsorption energies of Si atoms onto FeO surfaces are all obviously larger than that of the reducing gases,
making it extremely difficult for the reducing gases to remove O atoms from FeO surfaces, as the DFT
results show. Moreover, it is easier to form the Fe–O–Si phase on the FeO (110) surface since the adsorp-
tion energy of O–Si–O onto this surface is greater than that onto the FeO (100) and FeO (111) surfaces.
Additionally, the charge of the O (FeO) 2p orbital, the Si 3p orbital, as well as the 3s, 3p, and 3d orbitals
of the Fe atom take charge of the formation of Si–O–Fe bond.

KEY WORDS: reduction behavior; silica-hematite system; density functional theory (DFT); FeO surface;
adsorption energy.

is promoted at temperatures above 1 073 K and retarded at

1. Introduction
With the increasing shortage of high-quality raw materi-
als around the world, various beneficiation methods are
being developed for iron ores, especially for the high-silica
and low-iron ores, to meet the rapidly growing demand
of iron ores in the iron making industry.1,2) In particular,
China has more than 55 billion tons of this iron ore in the
iron grade range of 20–50%, accounting for 89% of total
iron ore reserves in China.3,4) Regarded as one of the most
refractory iron ore sources, this large resource is difficult to
be beneficiated effectively with existing mineral processing
technologies due to its complex mineral composition, high
silica content and other reasons.5)
SiO2-containing minerals found in iron ore are usually
regarded as detrimental by many ironmaking and steelmak-
ing operators. The studies relevant to the effects of SiO2
are summarized below. El-Geassy et al.6) found that the
various forms of SiO2, such as the crystalline (α -SiO2) or
amorphous forms, play an important role in determining
the materials’ reducibility during the reduction of Fe2O3
and FeO. N Shigematsu et al.7) found that with a small
amount of SiO2 dissolved in the FeO phase, the reduction
* Corresponding author: E-mail: zchuangcsu@126.com
DOI: https://doi.org/10.2355/isijinternational.ISIJINT-2018-613
temperatures below 1 003 K. In addition, above 1 473 K,8)
reduction of FeO is not accelerated by SiO2, but retarded
by the formation of the layer of dense iron on wüstite or by
the dense fayalite phase. M Bahgat, et al.9) observed that the
addition of silica decreases the porosity of wüstite compact
owing to the formation of iron silicate phases. Hyunsik Park
et al.10) investigated the influence of alumina and silica on
the reduction behavior of carbon composite pellet at 1 273
K, 1 373 K11) and 1 473 K12) by thermogravimetric analy-
sis. Wanho K, et al.13) indicated that the reduction rate and
reducibility under H2 are significantly higher than those
under CO when SiO2-containing (0–30 wt.%) compacts get
reduced at 1 273 K. Huang Z, et al.14) investigated the reduc-
tion behavior of low-iron and high-silica ore-coal composite
pellets at 1 143–1 263 K. Although the effect of SiO2 has
been well documented for many research techniques, the
exact underlying reasons for various performances are often
more difficult to access.
As a robust and accurate method, density functional theory
(DFT) is becoming more and more prevalent in the modeling
of adsorptions of different phase interfaces, including those
relevant to the chemical industry and metallurgical engineer-
ing.15,16) Du M F et al.17) carried out a study of fayalite with a
high content of iron in the initial layer of coal ash using the
GGA and PW 91 based on quantum chemistry. In this study

227 © 2019 ISIJ
 ISIJ International, Vol. 59 (2019), No. 2
regarding the characteristics of high silica, it is easy for the
SiO2–Fe2O3 system to form some low melting phases such as
Fe2SiO4, Fe2SiO4–SiO2, Fe2SiO4–FeO, and Fe2SiO4–Fe3O4.
The soft melting points of Fe2SiO4, Fe2SiO4–SiO2, Fe2SiO4–
FeO, and Fe2SiO4–Fe3O4 are only 1 478 K (1 205°C), 1 451
K (1 178°C), 1 451 K (1 178°C) and 1 415 K (1 142°C),
respectively, leading to a ring formation in the rotary kiln
and a disruption of normal operation.18,19) Another major
characteristic of this high-silica and low-iron ore is high fine-
grained dissemination. Within the iron ore used in our previ-
ous studies, process mineralogy tests showed that 95.73%
of the diameters of hematite grains were smaller than 37
μm and 39.94% diameters of the hematite particulates were
smaller than 10 μm.14,20,21) In summary, all of these charac-
teristics bring a great difficulty to the beneficiation of iron
resources and provide an opportunity for silica and hematite
particulates to concatenate tightly with each other. As we
know, elementary reaction steps, that is, the dissociation of
reactants and association to products, take place at the solid-
gas or solid-liquid interface. However, surface and electronic
properties of solids are often also significantly altered as par-
ticle sizes decrease.22) Thus, hematite and silica powder with
average particulate sizes of 7.172 μm and 7.920 μm, respec-
tively, were adopted to make briquettes for reduction roast-
ing in the experimental part of this study in order to simulate
the grain distribution states of fine-grained dissemination
of high-silica and low-iron ore to understand the influence
of different silica contents. For the theoretical experiments,
the ‘O–Si–O’ segment, a shared structure between SiO2 and
2FeO·SiO2, was employed for the DFT calculations accord-
ing to Fig. 1. The unit cell of SiO2 (as depicted in Fig.
1(a)) shows that silicon ions are tetrahedrally coordinated to
oxygens.23) Meanwhile, the 2FeO·SiO2 unit cell (as shown in
Fig. 1(b)) contains four formula units with 28 atoms (8 Fe,
4 Si, and 16 O). Silicon ions are tetrahedrally coordinated to
oxygens, whereas iron-ions occupy the centers of distorted
oxygen octahedra.17,24,25) Thus, DFT calculations based on
the periodic surface model has been performed in this paper,
which investigate the adsorption behaviors and properties
of O–Si–O onto three different FeO surfaces.
2.  Experimental Procedure
2.1.  Apparatus and Procedure
For the sample preparation, hematite powder was obtained
by roasting a magnetite concentrate from Columbia in air
at 1 173 K (900°C) for 1 hour to oxidize. The chemical
compositions of hematite powder and pulverized anthracite
(reductant) are shown in Tables 1 and 2, respectively. The
amount of coal addition in the mixture was determined
according to C/Fe mass ratio of 0.3 (i.e., mass ratio of fixed
carbon in the anthracite to reducible iron in hematite pow-
der was 0.3) as this was confirmed as adequate from the
previous studies.14,20,21) Besides, the bentonite content was
fixed at 1.0% of the total mass of the compacts. The silica
contents were correspondingly set to 1.5 wt.%, 6.0 wt.%,
30.0 wt.%, and 50.0 wt.% for the investigation of its impact
on reduction behavior. The carbon composite compacts used
in this study were composed of hematite powder, anthracite,
bentonite, and analytical SiO2 reagent chemicals ( ≥ 99.0%),
which were cylindrical in shape, 10 mm in diameter, 8–13
© 2019 ISIJ
Table 1.  Chemical composition of hematite powder (mass, %).
Fe2O3 FeO SiO2 Al2O3 CaO MgO MnO Na2O K 2O S P
95.13 1.52 1.53 0.78 0.69 0.11 0.05 0.06 0.03 0.01 0.02
Table 2.  Proximate analysis of pulverized anthracite (mass, %).
Category FC, ad M, ad A, ad V, ad S
Anthracite 82.54 3.14 10.57 6.68 0.21
(FC, ad: Fixed carbon (air dried basis); M, ad: Moisture (air dried basis);
A, ad: Ash (air dried basis); V, ad: Volatile matter (air dried basis))
mm in height, and 2.5 g ( ± 0.05 g) in weight. Then, the
samples were dried in air at 378 K (105°C) for 3 hours
to eliminate moisture. The mean particulate sizes of the
hematite and silica powders were 7.172 μm and 7.920 μm,
respectively.
The experimental procedure can be described as follows:
10–12 dried compacts, coupled with 60 g of coal powder
beneath and another 120 g of coal on the top of the com-
pacts, were used each time for carbothermic reduction.
Reductive roasting of the compacts was performed in a
shaft furnace in the temperature range of 1 223–1 373 K for
30–90 min. Reduced compacts were then cooled to ambi-
ent temperature in a nitrogen atmosphere. The metallization
ratios of the reduced compacts were measured after each
reductive roasting experiment. The metallization ratio (MR)
was evaluated with Equation:
M R  M Fe / TFe  100% ........................ (1)
where MFe is the metallic iron content and TFe is the total
weight of iron in the reduced compacts. The measurements
of MFe and TFe were corresponding obtained by FeCl3–
K2Cr2O7 and TiCl3–K2Cr2O7 volumetric methods.26)
After reduction, phase transfers of the reduced compacts
were analyzed by chemical phase dissolution measurements
and X-ray diffraction (XRD). The morphological evolution
and phase evolution were investigated by scanning electron
microscope (SEM) equipped with EDX.
2.2.  Computational Method and Models
In this work, all the calculations were performed with the
Cambridge Sequential Total Energy Package (CASTEP)27)
with a pseudopotential plane-wave approach based on DFT.
The electron ion-core interactions were described by an
OTFG ultra-soft pseudopotential, the most accurate calcula-
tion method at present, supplied with VASP of Si 3S23P2,
Fe 3s23p63d6, and O 2s22p4 states as valence states.28,29)
The generalized gradient approximation (GGA)30) with
the Perdew-Burke-Ernzerhof (PBE) exchange-correlation
functional31) applied to deal with the electron exchange
and correlation interaction. The solutions of Kohn-Sham
equations were represented by the plane-wave-basis with a
kinetic energy cutoff of 280 eV.32) The convergence toler-
ance energy, self-consistent iterative convergence accuracy,
max displacement, max force and convergence of internal
stress among atoms were 2.0 × 10 − 5 eV/atom, 2.0 × 10 − 5
eV/atom, 0.002 Å, 0.05 eV/Å and 0.1 GPa, respectively.
The Brillouin zone integration was performed in the
Monkhorst-Pack scheme using the k-point set of 2 × 2 ×
1 for adsorption studies.33,34) For the Brillouin zone inte-
228
 ISIJ International, Vol. 59 (2019), No. 2

Fig. 1. The side view of unit cell structure of SiO2 (a) and
2FeO·SiO2 (b). (Purple, red and green balls represent the
Fe, O and Si atoms, respectively.).

Fig. 5. XRD patterns of reduced compact with different silica

content at 1 323 K.

Fig. 2. The side view of 1 × 1 unit cell structure of FeO (a), FeO
(100) (b), FeO (110) (c), FeO (111) (d) and O–Si–O (e).
(Purple, red and yellow balls represent the Fe, O and Si
atoms, respectively.).

Fig. 3. Effect of temperature and time on metallization ratio of Fig. 6. SEM-EDX analysis of reduced compact with different sil-
reduced compact. ica content at 1 323 K: 6% silica (a), 30% silica (b), and
50% silica (c).

Fig. 4. Valence state distribution of reduced compact with differ- Fig. 7. Compressive strength of reduced compact with different
ent silica content at 1 323 K. silica content at 1 223–1 323 K.

229 © 2019 ISIJ
 ISIJ International, Vol. 59 (2019), No. 2

Fig. 12. Electron distribution and Mulliken charges of atoms for

adsorption of O–Si–O on FeO (110) surface: top view
before adsorption (a), side view before adsorption (b),
and side view after adsorption (c) (Purple, red and yellow
balls represent the Fe, O and Si atoms, respectively).
Fig. 8. Concentration of reducing gas needed for reduction using
CO.

Fig. 10. Electron distribution and Mulliken charges of atoms for

adsorption of O–Si–O on the FeO (100) surface: top view
before adsorption (a), side view before adsorption (b),
and side view after adsorption (c) (Purple, red and yellow
balls represent the Fe, O and Si atoms, respectively).

Fig. 13. PDOS of the Si before adsorption (a), the adsorbed Si (b),
the clean O of FeO before adsorption (c) and the adsorbed
O (d) for adsorption of O–Si–O on FeO (110) surface.

Fig. 14. Electron distribution and Mulliken charges of atoms for

adsorption of O–Si–O on FeO (111) surface: top view
Fig. 11. PDOS of the Si before adsorption (a), the adsorbed Si (b), before adsorption (a), side view before adsorption (b),
the clean O of FeO before adsorption (c), the adsorbed O and side view after adsorption (c) (Purple, red and yellow
(d), and the adsorbed Si/O (e). balls represent the Fe, O and Si atoms, respectively).

© 2019 ISIJ 230
 ISIJ International, Vol. 59 (2019), No. 2
grations, a 12 × 12 × 12 Monkhorst-Pack grid of special
k-points was used.
As a crystal with face-centered cubic structure, the solid
FeO used in this study has a cell parameter of 4.307 Å,35) in
which the Fe and O atoms adopt an octahedral coordination.
All Fe–O bond lengths were found to be 2.166 Å (Fig. 2(a)),
which coincides well with Zhong H’s theoretical result of
2.166 Å.36) As shown in Figs. 2(b), 2(c) and 2(d), FeO (100),
FeO (110) and FeO (111) surfaces were chosen. 1 × 1 cells38)
with five relaxed atomic layers were adopted.37) To avoid
the interaction between neighboring slabs, the vacuum space
was set to 15 × 15 × 15 Å, which had been proven to be
large enough in previous studies.38) A structurally optimized
O–Si–O segment with Si–O bond lengths of 1.549 Å and
a bonding angle of 180° was obtained in the same vacuum
space, as depicted in Fig. 2(e), before adsorbing onto the
FeO surface.
The adsorption energies (Ead) of an O–Si–O fragment
approaching the clean (100), (110) and (111) FeO surfaces
were each calculated as the total energy difference of the
energy of an isolated O–Si–O segment (EO–Si–O) and the
energy of the FeO surface before adsorption (Eslab),
E ad  E system  E OSiO  E slab .................... (2)
where Esystem, EO–Si–O, and Eslab are the energy of the adsorp-
tion system, the isolated O–Si–O segment and the clean
surface, respectively.
3.  Results and Discussion
3.1.  Influence of Silica on Metallization at 1 223–1 373
K granules (about 30–50 μm) and a distinct boundary between
The metallization ratios of the reduced compacts with
SiO2 contents of 1.5–50 wt.% in the temperature range
of 1 223–1 373 K (950–1 100°C) for 30 min are given in
Fig. 3. It can be observed from the line chart that when the
compact with a SiO2 content of 1.5% was roasted at 1 223
K, the metallization ratio was lower than 60%. This value
greatly increased when the temperature rose to 1 373 K,
reaching 93.7%, and increases by 35.2% compared to 1 223
K. Additionally, increasing the SiO2 content to 50 wt.% led
to a sharp diminution of the metallization ratio, even when
the compact was roasted at 1 373 K. This value decreased
to 60.9% for a SiO2 content of 50% at 1 373 K, indicating
that SiO2 produces a tremendous inhibition effect on the
metallization ratio of reduced compacts. Moreover, when
a compact with a 50 wt.% of SiO2 was reduced at 1 223
K, the metallization ratio was extremely low, only 44.3%.
Therefore, the results imply that silica within the iron oxide
and solid carbon significantly influences the formation
of metallic iron both at higher temperatures and at lower
temperatures.
A more comprehensive study of the distribution of
valence states within the iron phase in the reduced compacts
at 1 323 K was carried out via chemical phase dissolution,
presented in Fig. 4. As can be seen, the Fe0 state accounts
for most of the total iron of the reduced compact with dif-
ferent silica contents, followed by Fe2 + and Fe3 + . It is quite
clear that the percentage contents of both Fe2 + and Fe3 + are
gradually promoted with increasing silica content, while the
Fe0 changes in the opposite trend, simultaneously.
231
3.2.  Influence of Silica on Phase and Morphology Evo-
lution at 1 323 K
Compacts with different contents of silica reduced at
1 323 K for 30 min were characterized by XRD to under-
stand the phase transformation upon increasing the silica
content, as presented in Fig. 5. The XRD pattern showed
the major phase of metallic iron coexists with minor silica
in the reduced compact with 6 wt.% silica, implying that the
repercussions for 6 wt.% silica usage in compact are almost
negligible to the reduction process. A further 30 wt.% rise
of silica content leads to the formation of cristobalite and
fayalite, which inevitably hinders the separation of elemen-
tal Fe and Si. Furthermore, the increase of silica content
from 30% to 50 wt.% significantly strengthens the intensity
of cristobalite and fayalite diffraction peaks. Meanwhile,
the diffraction peak corresponding to metallic iron weak-
ens with the increase of silica content, which corresponds
directly with the results in Fig. 4. Thus, the reason for the
phenomenon of diminution of the metallization ratio is con-
sidered to be the formation of fayalite (Fe2SiO4), which is
more difficult to be reduced by carbon.
The microstructure (SEM) and energy spectrum analy-
sis of the reduced compact with different silica contents
reduced at 1 323 K for 30 min were characterized, as shown
in Fig. 6, to reveal the intrinsic morphological evolution and
its relationship to silica content. A compact platy structure
can be widely observed in a reduced compact with a silica
content of 6.0%, as shown in Fig. 6(a). It is mainly com-
posed of metallic iron and wüstite after being identified by
EDX. In addition, analysis of mineralogical constitution and
the structure of the compact showed that larger iron phase
the iron phase and the silicon-rich slag phase form (Fig.
6(a)). Compared to Figs. 6(b), 6(c), it created a favorable
condition for subsequent milling-magnetic separation. Silica
content from 6 to 30 wt.% contributed to the fragmentary
structure with fine iron granules (about 10 μm), as shown
in Fig. 6(b). Additionally, the Fe–Si–O phase (FeO·3.7SiO2;
FeO·3.2SiO2; 2FeO·SiO2) and the independent silica par-
ticulates confirmed by EDX analysis became more and
more apparent. A further 50 wt.% rise of SiO2 content led
to a sharp diminution of the iron phase dimension (only 5
μm) and a sharp increase of Fe–Si–O phase (FeO·20.1SiO2;
1.6FeO·SiO2), as shown in Fig. 6(c). Moreover, the subsid-
ence holes in the reduced compact diminished gradually
with the increase of silica content. To summarize, it is clear
that silica plays a crucial role in the microstructure and
phase evolution of these materials.
3.3.  Influence of Silica on Compressive Strength of
Reduced Compact
The compressive strength of the reduced compacts with
different silica contents at 1 223–1 323 K are shown in Fig.
7.
It can be seen that the compressive strength of the
reduced compact with a silica content of 1.5% is relatively
low (400–1 100 kPa) at all of the roasting temperatures.
Moreover, the value reached 3 215 N at 1 323 K when
6.0% silica is added and increases by 2 731 N compared to
1 223 K. A further 30 wt.% rise of silica content brought
about a sharp enhancement of the compressive strength
© 2019 ISIJ
 ISIJ International, Vol. 59 (2019), No. 2
(2 000–3 000 kPa) of the compact, even when roasted at
1 223 K, as depicted in Fig. 7. Furthermore, it is obvious
that the value (4 000–8 000 kPa) continued to increase
with increasing silica content, demonstrating that melts of
low-temperature eutectic point formed abundantly. There-
fore, the results suggest that the compressive strength of
the reduced compact is enhanced effectively by silica, par-
ticularly when the silica content is above 30%, making the
diffusion resistance of the reducing gases larger and larger,
which is another reason for the diminution of the metalliza-
tion ratio.
3.4.  Mechanism Analysis of Effect of Silica on Reduc-
tion
3.4.1.  Reaction Mechanism of Iron Ore Reduction with
Silica
The main reduction of carbon composite compact takes
place through the reaction between wüstite and anthracite in
the solid state at 1 223–1 373 K (950–1 100°C). The reaction
mechanism has been studied by numerous researchers.39–42)
FeO  C  Fe  CO
............... (3)
G   147 900  150.24 T (J / mol)
FeO  CO  Fe  CO2
............... (4)
G   22 800  24.26 T (J / mol)
C  CO2  2CO
............... (5)
G   172 423  175.69T (J / mol)
2 FeO  SiO2  2 FeO·SiO2
................ (6)
G   76 415  33.79T (J / mol)
2 FeO·SiO2  2C  2 Fe  SiO2  2CO
............. (7)
G   353 922  338.96 T (J / mol)
1 / 2  2 FeO  SiO2   CO  Fe  1 / 2SiO2  CO2
..... (8)
G   6 261  5.01T (J / mol)
The whole reduction process is a perfect cycle: First
of all, although the solid-solid interaction (Eq. (3)) con-
tributes only a small part to the total reduction process
at 1 223–1 373 K, the reaction cycle is initiated by this
reaction. Then, the gas immediately reacts with wüstite as
shown in Eq. (4), followed by the generation of CO in Eq.
(3). Finally, this solid-gas reaction generates CO2 gas that
is used for a source of the Boudouard reaction seen in Eq.
(5).11) However, the reaction of FeO to Fe, which should
take place, seems to be substantially inhibited by the added
amount of silica which is known to form high concentra-
tion in FeO–SiO2 melt.12) The concentrations of CO used
as a reducing gas needed for the reduction reactions are
demonstrated in Fig. 8. It can be observed from the line
chart that, it is harder for the FeO/Fe reaction to proceed
forward compared with reactions of Fe2O3/Fe3O4 and Fe3O4/
FeO on account of a far higher CO concentration require-
ment.43) When considering Figs. 3 and 7, we found that
the metallization ratio of the reduced compacts with 50%
silica are extremely low, only 44.27–60.94% when roasted
at 1 223–1 373 K. Meanwhile, the compressive strengths
were fairly high, 3 947–8 111 N. The results confirm that
the CO concentration around some FeO particulates in the
© 2019 ISIJ
compacts is most probably lower than the required level
for the FeO particulates that are surrounded by massive,
fine-grained disseminated silica particulates (shown in Fig.
9) and the newly formed silicate melts. Thus, the intermedi-
ate FeO reduction will inevitably react with silica/silicate,
particularly when the silica content is high, to form the
Fe–Si–O phase, shown in Eq. (6). P. Semberg43) and A. A.
Elgeassy44) also reported the same observation. Furthermore,
Eqs. (7), (8) and Fig. 8 indicate that, once FeO transformed
into Fe2SiO4, it can hardly be reduced to metallic iron again.
3.4.2.  Adsorption Behaviors of O–Si–O on FeO Surface
As depicted in Fig. 9, the volume ratio of silica to hema-
tite increases gradually with the increase of silica content.
By computation, the values are 49:51 and 69:31, respec-
tively, when the silica content in the SiO2–Fe2O3 system
is 30% and 50%. Moreover, the d50 of silica and hematite
used in this study is correspondingly 7.920 μm and 7.172
μm identified by particulate size analysis. Thus, the granule
count ratios of silica to hematite are 41:59 and 62:38 when
the silica content is 30% and 50%, respectively. Conse-
quently, silica and hematite particulates are in tight conjunc-
tion with each other in compacts, creating an opportunity
for the adsorption and dissolution especially when melts of
low-temperature eutectic points form.
(1)  Adsorption of O–Si–O onto the FeO (100) Surface
The adsorption of O–Si–O on the FeO (100) surface was
calculated for the Si–O (FeO) top site, as shown in Fig. 10.
The results implied that the bonding angle of the ‘O–Si–O’
segment changed (from 180° to 102.948°) distinctly for the
configuration of the Si atom adsorbing directly to the O
top site. The ‘O–Si–O’ segment was chemisorbed onto the
surface, forming a Si–O bond with a bond length of 1.889 Å
and an adsorption energy of − 6.25 eV. Compared with Figs.
10(b) and 10(c), these results show that a slight relaxation
occurs in the adsorbed surface. Moreover, the relaxation of
the second and the third inter-lattice spacing is found to be
quite different from that of the pure optimized FeO (100)
surface, with an expansion instead of a contraction of atomic
layers. As shown in Fig. 10(c), the distance between the
adsorbed O atom and the second layer Fe atom is elongated
from 1.831 Å to 3.015 Å, demonstrating the formation of a
new Si–O bond and the breakage of an original Fe–O bond.
Meanwhile, it is worth noticing that the O atom on the FeO
(100) surface is raised slightly due to the adsorption of the
‘O–Si–O’ segment. Also, the distance between the adsorbed
O atom and the adjacent Fe atom on the first layer is short-
ened from 1.903 Å to 1.890 Å, indicating that the binding
energy between Fe and O on the first layer is increased after
adsorption, meaning the reducing deoxygenation process
Fig. 9. Schematic diagram of particulate distribution in silica-
hematite compact.
232
 ISIJ International, Vol. 59 (2019), No. 2

will become more difficult. In addition, the Si–O bond of surface was investigated as well by approaching the Si atom
O–Si–O is activated and elongated, which are correspond- onto the O top site, as shown in Fig. 12. In Fig. 12(c), the
ingly 1.701 Å and 1.710 Å in length and longer than that of O–Si–O is chemisorbed onto the surface via Si–O bond-
the optimized O–Si–O (1.549 Å). Hence, the present study ing after adsorption, making the surface relaxation more
confirms that the interaction between the O atom of the first apparent. Additionally, the calculation results imply that
layer and Si intensifies after adsorption, while the interac- the Si–O bond length is 1.686 Å and the adsorption energy
tion between the O atom of the first layer and the Fe atom is − 7.01 eV, which is stronger than that of Si adsorbing
of the second layer weakens substantially. onto the FeO (100) surface. Meanwhile, the bonding angle
The total atomic charges from the natural bond orbital of the O–Si–O changed from 180° to 150.148°, and the
charge analysis for O–Si–O adsorbed on FeO (100) at the Si–O bond of O–Si–O is activated and elongated, which are
Si–O top site are presented in Table 3. After adsorption, the correspondingly 1.706 Å and 1.739 Å in length and longer
delocalization of the electron cloud of the outermost layers than that of the optimized O–Si–O (1.549 Å). In addition,
of Si and Fe atoms makes the O atoms of the O–Si–O seg- the Fe–O bond length had been stretched slightly from 1.779
ment and the O atom of the first layer negative. From the Å to 1.862 Å, with the raising of the O atom on the surface
results in the table, we can see that the charges of the 3p being due to the adsorption of Si, indicating a new Si–O–Fe
orbital of the Si atom and the 3d orbital of the Fe1 atom bond formation.
change in the adsorption process. The main reason for the The total atomic charges from the natural bond orbital
adsorption is the interactions between the 2p orbital of the charge analysis for O–Si–O adsorbed on FeO (110) at Si–O
O3 atom and the 3p orbital of the Si atom consorting with top site are presented in Table 4. From the results in the
the 3d orbital of the Fe1 atom. It can be concluded that the table, the delocalization of the electron clouds of outermost
adsorption of Si on the FeO (100) surface causes charge layers of the Si and Fe atom makes the O atom of the first
transference from the 3p orbital of the Si atom and the 3d layer negative. Additionally, the charge of the 2p orbital of
orbital of the Fe1 atom to the 2p orbital of the O atom. the O atom, the 3p orbital of the Si atom, as well as the 3s,
Further investigation into the type of bonding mechanism 3p, and 3d orbitals of the Fe atom are responsible for the
for adsorption of the O–Si–O segment onto the FeO (100) new Si–O–Fe bonding. As a comparison, PDOS of the Si
surface can be obtained by analyzing the partial density of atom, the O atom and Si–O are shown in Fig. 13. Orbital
states (PDOS) of O–Si–O and FeO (100) surface before and hybridization and bonding characteristics are analyzed
after adsorption, as shown in Fig. 11. The Fermi energy according to the interaction between Si atoms and O atoms.
level was set as zero when plotting. In Figs. 11(a) and 11(b), In Fig. 13(e), there is a strong resonance between the O
the electronic state locates in the energy range of − 2.5 to 2p band and the Si 3p band in the energy range of − 10.0
0 eV and 5.0 to 12.5 eV, which is the main contribution of to − 2.0 eV, implying that the interaction between the O 2p
the 3p orbital of the Si atom before adsorption, while the orbital and the Si 3p orbital is relatively strong, meaning a
3p band peak splits into three peaks and shifts downward hybridized orbital has formed.
towards the Fermi level after adsorption. Evidently, the state (3)  Adsorption of O–Si–O onto the FeO (111) Surface
density of Si atom weakens. As a comparison, the results of Here, just like the adsorptions of O–Si–O onto the (100)
Figs. 11(c) and 11(d) lead to a similar conclusion that the 2p and (110) FeO surfaces, adsorption of the O–Si–O onto the
orbital peak of the O atom splits into two peaks and shifts FeO (111) surface was investigated by approaching the Si
downward towards the Fermi level as well, making the new atom onto the O top site, as shown in Fig. 14. In Fig. 14(c),
Si–O bond more stable. Thus, it indicates clearly that the the O–Si–O is chemisorbed to the O top site by Si–O bond-
3p band of Si and the 2p band of O are responsible for the ing. After adsorption, the new Si–O bond length is 2.390
Si–O bonding, corresponding to the results of orbital charge Å and the Si–O bond lengths of the O–Si–O are elongated
population analysis. from 1.549 Å to 1.962 Å and 1.967 Å, respectively. The
(2)  Adsorption of O–Si–O onto the FeO (110) Surface adsorption energy of this configuration is − 5.72 eV accord-
Adsorption of the O–Si–O segment onto the FeO (110) ing to calculation, which is the smallest adsorption energy
value among that of the above three configurations.
Table 3. Orbital charge population analysis of O–Si–O adsorbed
(4)  Different Adsorption Behaviors of O–Si–O onto
on FeO (100) surface. FeO Surfaces
Comparing the adsorption behaviors of O–Si–O onto
Site Species s p d Total
three different FeO surfaces, three different characteristics
Free O1 1.95 5.04 0.00 6.99
are obtained. Firstly, the adsorption energies of O–Si–O
O2 1.95 5.04 0.00 6.99
onto FeO surfaces are all larger than that of H2 ( − 0.65 eV)
Si 0.72 1.29 0.00 2.02
and CO ( − 1.41 eV),32) implying that O–Si–O is more easily
Clean O3 1.92 4.66 0.00 6.58
and steadily adsorbed onto FeO surfaces than reducing gases
Fe1 0.56 0.10 6.68 7.35 (H2 or CO). Thus, it is difficult for H2 and CO to remove O
Fe2 0.58 0.22 6.71 7.51 atoms from FeO surfaces when it is adsorbed by O–Si–O,
System O1 1.87 5.15 0.00 7.02 which is corroborated by the experimental results of Fig.
O2 1.86 5.16 0.00 7.02 4. Secondly, the first layer O (FeO) atoms on different
O3 1.91 4.75 0.00 6.66 FeO surfaces are all raised slightly after adsorption. Also,
Si 0.76 1.17 0.00 1.93 the bond lengths between the adsorbed O atoms and the
Fe1 0.38 0.29 6.57 7.25 second layer Fe atoms are clearly elongated, demonstrating
Fe2 0.66 0.20 6.74 7.60 the formation of a new Si–O bond and the breakage of the

233 © 2019 ISIJ
 ISIJ International, Vol. 59 (2019), No. 2

Table 4. Orbital charge population analysis of O–Si–O adsorbed Acknowledgments

on FeO (110) surface. The authors would like to express thanks to the National
Site Species s p d Total Science Fund for Distinguished Young Scholars of China
Free O1 1.95 5.04 0.00 6.99 (Grant No. 50725416) for financial support of this research.
O2 1.95 5.04 0.00 6.99
Si 0.72 1.29 0.00 2.02 REFERENCES
Clean O3 1.92 4.67 0.00 6.59 1) U. Srivastava and S. K. Kawatra: Miner. Process. Extr. Metall. Rev.,
Fe 0.45 0.23 6.75 7.43 30 (2009), 361.
2) S. X. Song, E. F. Campos-Toro, Y. M. Zhang and A. Lopez-
System O1 1.88 5.10 0.00 6.98 Valdivieso: Int. J. Miner. Metall. Mater., 20 (2013), 113.
O2 1.90 4.91 0.00 6.82 3) Y. Wang, S. W. Xing, Z. J. Zhang, Y. B. Ma and Y. Zhang: Multi-
O3 1.89 4.96 0.00 6.85 purp. Util. Miner. Resour., 10 (2014), 15.
4) Y. F. Yu: Conserv. Util. Miner. Resour., 12 (2005), 43.
Si 0.81 1.22 0.00 2.03 5) Y. S. Sun, Y. X. Han, Y. F. Li and Y. J. Li: Int. J. Miner. Metall.
Fe 0.33 0.14 6.54 7.01 Mater., 24 (2017), 123.
6) A. A. Elgeassy, K. A. Shehata and S. Y. Ezz: Iron Steel Int., 50
(1977), 329.
7) N. Shigematsu and H. Iwai: Tetsu-to-Hagané, 73 (1987), 1329.
original Fe–O bond. Thirdly, the configuration of O–Si–O 8) N. Shigematsu and H. Iwai: Tetsu-to-Hagané, 79 (1993), 920.
9) M. Bahgat, K. S. A. Halim, M. I. Nasr and A. A. El-Geassy: Ironmak-
adsorbing to the FeO (110) surface is the most stable state ing Steelmaking, 35 (2008), 205.
( − 7.01 eV) among the three examined sites, indicating 10) T. Inami and K. Suzuki: ISIJ Int., 43 (2003), 314.
that it is easier for FeO (110) to form the Fe–O–Si phase. 11) H. Park and V. Sahajwalla: ISIJ Int., 54 (2014), 1256.
12) H. Park and V. Sahajwalla: ISIJ Int., 54 (2014), 49.
Moreover, the surface relaxation on the FeO (110) surface 13) K. Wanho, L. Youngseok and S. Inkook: ISIJ Int., 52 (2012), 1463.
is the most obvious due to a stronger interplay between Si 14) Z. C. Huang, R. H. Zhong, L. Y. Yi, T. Jiang, L. M. Wen and Z. K.
Liang: Metall. Mater. Trans. B, 49 (2018), 411.
atoms and the surface. 15) H. Zenia, K. Lounis, E. H. Megchiche and C. Mijoule: Comput.
Mater. Sci., 124 (2016), 428.
16) J. P. Lu, M. R. Albert, S. L. Bernasek and D. J. Dwyer: Surf. Sci.,
4. Conclusions 215 (1989), 348.
17) M. F. Du, G. L. Lu and T. Zhou: Adv. Mater. Res., 156 (2010), 1430.
The effect of silica on the reduction behaviors of a 18) J. Y. Fu, T. Jiang and D. Q. Zhu: Sintering and Pelletizing, Central
South University of Technology Press, Changsha, (1996), 36.
hematite-carbon composite compact at 1 223–1 373 K 19) D. Q. Zhu, T. J. Chun, J. Pan and J. L. Zhang: Int. J. Miner. Process.,
(950–1 100°C) was investigated. DFT calculations have 125 (2013), 51.
20) Z. K. Liang, Z. C. Huang, L. Y. Yi and R. Zhong: 9th Int. Symp. on
been employed to investigate the adsorption behaviors of High Temperature Metallurgical Processing, The Minerals, Metals &
the ‘O–Si–O’ segment onto three FeO surfaces for further Materials Society, Pittsburgh, PA, (2018), 465.
understanding of the mechanism. The following conclusions 21) Z. C. Huang, L. M. Wen, R. H. Zhong and T. Jiang: 7th Int. Symp.
on High Temperature Metallurgical Processing, The Minerals, Metals
can be drawn from this study. & Materials Society, Warrendale, PA, (2016), 461.
(1)  The metallization ratio of carbon composite com- 22) S. E. De, M. M. van Schooneveld and F. Cinquini: Angew. Chem.
Int. Ed., 50 (2011), 1584.
pact is influenced by silica contents. Silica decreases the 23) B. W. Van Beest, G. J. Kramer and R. A. Van Santen: Phys. Rev.
metallization ratio by hindering the process of reducing FeO Lett., 64 (1990), 1955.
to Fe and facilitating the reaction of FeO to Fe–Si–O phases 24) M. Cococcioni, A. D. Corso and S. D. Gironcoli: Phys. Rev. B, 67
(2003), 552.
(FeO·20.1SiO2; FeO·3.7SiO2; FeO·3.2SiO2; 1.6FeO·SiO2; 25) N. P. Hou, M. F. Du, J. Li, G. H. Wu and X. J. Wu: Mater. Rev., 24
2FeO·SiO2) according to the results of XRD, SEM-EDX (2010), 76.
26) R. J. Saikkonen and I. A. Rautiainen: Bull. Geol. Soc. Finl., 65
and chemical analysis. Moreover, the size of metallic iron (1993), 59.
granules in the reduced compacts diminishes gradually and 27) M. C. Payne, M. P. Teter, D. C. Allan, T. A. Arias and J. D.
Joannopoulos: Rev. Mod. Phys., 64 (1992), 1045.
the boundary between the iron phase and the silicon-rich 28) G. J. Kresse and D. P. Joubert: Phys. Rev. B, 59 (1999), 1758.
slag phase becomes less and less obvious with increasing 29) J. P. Perdew, J. A. Chevary and S. H. Vosko: Phys. Rev. B, 46 (1993),
silica content, which greatly increases the contact probabil- 6671.
30) J. A. White and D. M. Bird: Phys. Rev. B, 50 (1994), 4954.
ity of SiO2/liquid phases and FeO. 31) T. Ossowski and A. Kiejna: Surf. Sci., 637 (2015), 35.
(2)  For the three adsorption sites, the adsorption ener- 32) H. Zhong, L. Y. Wen, J. L. Li, J. Xu, M. L. Hu and Z. Q. Yang:
Powder Technol., 303 (2016), 100.
gies of Si atoms onto FeO surfaces are all obviously larger 33) A. Stukowski and K. Albe: Modell. Simul. Mater. Sci. Eng., 18
than that of reducing gases, making it very difficult for (2010), 15.
reducing gases to remove O atoms from FeO surfaces, 34) S. W. Mai, G. D. Zhou and W. J. Li: Advanced Inorganic Structural,
Chemistry Peking University Press, Beijing, (2006), 292.
especially when Si–O–Fe bonding forms. Moreover, the 35) H. S. Cheng, D. B. Reiser and S. Dean: Catal. Today, 50 (1999), 579.
charge of the 2p orbital of the O atom, the 3p orbital of the 36) J. Song, X. Niu, L. Ling and B. Wang: Fuel Process. Technol., 115
(2013), 26.
Si atom, as well as the 3s, 3p, and 3d orbital of the Fe atom, 37) C. Dong, S. Sheng, Q. Wu, Q. Lu, Y. Zhao, X. Wang and J. Zhang:
are responsible for the new Si–O–Fe bond according to the Appl. Surf. Sci., 257 (2011), 8647.
orbital charge population analysis. 38) Y. K. Rao: Metall. Trans., 2 (1971), 1439.
39) E. T. Turkdogan and J. V. Vinters: Metall. Trans., 3 (1972), 1561.
(3)  It is easier for the FeO (110) surface to form a 40) J. Moon and V. Sahajwalla: Metall. Mater. Trans. B, 37 (2006), 215.
Fe–Si–O phase since the adsorption energy of O–Si–O onto 41) J. Yang, T. Mori and M. Kuwabara: Trans. Iron Steel Inst. Jpn., 47
(2007), 1394.
this surface is greater than that onto the Fe (100) and FeO 42) N. S. Srinivasan and A. K. Lahiri: Metall. Trans. B, 8 (1977), 175.
(111) surfaces. In addition, a strong resonance between the 43) P. Semberg, A. Rutqvist and C. Andersson: ISIJ Int., 53 (2013), 391.
44) A. A. Elgeassy, M. I. Nasr, A. A. Omar and E. A. Mousa: ISIJ Int.,
O 2p orbital and the Si 3p orbital and their corresponding 48 (2008), 1359.
hybridized orbital in the energy range of −10.0 to −2.0 eV
are observed when a Si atom adsorbs onto the FeO (110)
surface, which takes charge of the formation of a Si–O bond.

© 2019 ISIJ 234