Journal of Alloys and Compounds 650 (2015) 741e747

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Experimental research on mechanism and process of direct iron

making reduction of mechanically milling scale with coal
S. Osman Yilmaz a, Tanju Teker b, *
a , Turkey
Namık Kemal University, Faculty of Engineering, Department of Mechanical Engineering, 59860, Çorlu, Tekirdag
b
University of Adıyaman, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 02040, Adıyaman, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: This study delved into the fundamental mechanisms of a mill scale reduction. To achieve this objective,
Received 20 April 2015 the DRI process was applied to facilitate the mechanical milling of coal-scale mixtures. Temperatures of
Received in revised form 700e1000
C were used to sinter the mechanically milled coal-scale mixtures. The powders were sub-
7 July 2015
jected to scanning electron microscopy (SEM) and X-ray diffraction (XRD). In order to identify the
Accepted 19 July 2015
Available online 31 July 2015
reduction of milled scale-coal mixture with the temperature, iron phase analytical techniques and the
XRD were used. The differential thermal analysis (DTA) technique was used to determine the mea-
surements of the thermal property. Based on the findings of the experiments, it was concluded that coal
Keywords:
Mill scale
devolatilisation and scale reduction forms concurrently when the mixture is being heated. By 40 h
Coal milling, the milled coal-scale mixture's reduction start temperature decreased to 750
C.
Thermal analysis © 2015 Elsevier B.V. All rights reserved.
Iron ore reduction

1. Introduction
Traditional iron making techniques reduce iron ores of metallic
iron in blast furnaces. These methods require separate coke making
and sintering plants. Coals used in coke making are classified as
premium with higher costs and limited reserves. Much of the
recent developments in the field have been focused on applying
lower and cheaper grade of coals leading to the development of a
number of new emerging in direct reduction iron making (DRI)
technologies [1]. The largest advantage of the DRI technologies
relies on the fact that DRI does not require coke making and
sintering. Both coke making and sintering, being at the front end of
the conventional blast furnace iron making technology, are
considered as costly for the new process construction and are
consistently causing environmental concerns. The DRI process, on
the other hand, consists of carbothermic reduction of iron oxide
directly with the volatiles liberated during coal devolatilisation as
well as the carbon monoxide regenerated from coal char. In addi-
tion to, DRI process it is possible to produce iron from scale at solid
state conditions. This process provides an advanced utilization
opportunity for the low operational temperatures that means,
800e900
C, a temperature lower than sintering temperatures
* Corresponding author. Tel.: þ90 416 2233800; fax: þ90 416 2233809.
E-mail address: tteker@adiyaman.edu.tr (T. Teker).
[2e4]. This process concerns milling coke with ore and following
reduction process. Mechanical milling (MM) introduces high en-
ergy into the material being processed. This energy can be stored in
the material as atomic disorder and/or grain boundaries, i.e.,
DGmilling ¼ DGdisorder þ DGgrain boundaries. The atomic disorder in an
intermetallic can be manifested in three different ways [1e11].
Firstly, the two atomic species involved can occupy the “wrong”
sublattices and this is referred to as anti-site disorder. This in-
troduces strain into the lattice [4,5]. Secondly, triple-defects can be
generated. In an equiatomic compound and this is anti-site disor-
der. This leads to the presence of vacancies in the lattice to maintain
the stoichiometry. Thus, vacancies on the sublattice in combination
with anti-site atoms in a ratio of 2:1 constitute the triple defects.
Third, there could also be a redistribution of interstitial wherein the
interstitial atoms in the octahedral sites are transferred to the
tetrahedral sites. Additionally, grain refinement increases the grain
boundary area and this also raises the free energy of the system.
The sum of the energy of these two effects (disordering and crea-
tion of grain boundaries) will be the total energy introduced into
the material during milling [6e12].
The aim of this work is to investigate the effect of mechanical
milling on coal-scale reaction temperatures of the mixtures during
heating. Thermal properties, and iron phase changes during heat-
ing of the mixtures were determined, through which fundamental
insights into coal and scale behavior.

http://dx.doi.org/10.1016/j.jallcom.2015.07.172
0925-8388/© 2015 Elsevier B.V. All rights reserved.
742 S.O. Yilmaz, T. Teker / Journal of Alloys and Compounds 650 (2015) 741e747
2. Materials and methods
2.1. Experimental material
The main materials that were used in this experiment were coal
and mill scale. Table 1 illustrates the chemical composition of coal
as established by this study. The coal was found to have volatile
matter and ash in air-dry base of 33.5 wt.% and 6.5 wt.%, respec-
tively. In terms of daff base, it was found to have 85.1% C, 6.6% O,
5.5% H, 2.1% N, and 0.7% S. The byproduct was comprised of 62.1%
Fe, 4.33% SiO2 and 1.98% Al2O3.
2.2. Experimental methods
Prior to the initialization of the experiments, both samples were
dried for 2 h under vacuum at a temperature of 80
C. The average
particle size of coal was 80 mm while that of the scale was 50 mm.
A ratio of the mass of coal and scale mixture used in the study was
25:75. The first step of preparing the samples entailed milling the
mill scale and coal powders mechanical mixture using a high-
energy ball (Table 2), under argon atmosphere, in an attrition
made of hardened steel vial and balls. In the course of the experi-
ments, the milling settings were kept constant (i.e. a 30:1 ball-to-
powder mass ratio, a 600 rev/min speed of rotation and a
30e40e60 h milling time). The powders were subjected to scan-
ning electron microscopy (SEM: JEOL JSM 7001F) and X-ray
diffraction (XRD). At room temperature, the patterns XRD were
acquired by means of an XRD-6000 which had a Cu Ka/tube, 40 MA
current, 40 kV voltage, and a wave length of a ¼ 1.54056 Å. The
differential thermal analysis (DTA) technique was used to deter-
mine the thermal properties. The Perkin Elmer A 400 atomic ab-
sorption spectrometer was used for the determination of
metallization.
3. Results
Mechanical milling is a strategy that can be used to reduce metal
oxides when combine with more reactive elements at room tem-
perature. The process in reactivity literature is referred to mecha-
nosynthesis or mechanochemical synthesis [13]. Reduction process
is also called displacement reaction because one element is dis-
placed by another. Displacement reactions are some the most
common form of mechanosynthesis reactions commonly studied in
the literature.
This process involves two metals, whereby, one is more reactive
than the others. For example, a metal oxide (MO) when mix with a
more reactive metal (reductant R), is reduced to pure metal. It is
observed that all reactions involving solids lead to a development
of a product phase (s) at the interphases of the reactants. In regard,
during the reaction as the product increases, the reaction process
slows down. During the reactions, the reactant atoms diffuse
through the product phase, creating a barrier that reduces the rate
of reactions. The rate of the reaction depends on the extent to
which the reactant atoms can collide to initiate the process [14].
However, in order to increase the rate of reactions increase of the
temperature of the reactant is required. Additionally, metal alloying
is yet another strategy possible to increase the rate reactions ki-
netics in reduction processes substantially. Metal alloying increases
Table 1
Chemical composition of the coal used in experiments.
C H N S
Coal 76.35 5.5 2.1 0.63
Table 2
Mechanical milling time and sintering temperature of the samples.
Sample S1 S2 S3 S4 S5 S6 S7 S8 S9


Sintering temp, C 800 850 900 800 850 900 800 850 900
Sintering time, h 1 1 1 1 1 1 1 1 1
Mechanical milling time, h 30 30 30 40 40 40 60 60 60
the surface area for reactions by reducing the size of the reactants.
The size reduction using this metal alloying is achieved through the
process of welding and fracturing of powder particles. The
increased surface area for the reactions increases the chances for
the particles to collide and initiate the reactions without the need
for particle diffusion through the produce layers. Consequently, the
reactions that take place at extremely high temperature can occur
at a lower temperature, or even without heat application using the
metal alloying method. Apart from increasing the surface area, the
metal alloying method also increases the rate of reaction through
increasing the density of the particles, which in turn increases the
rate of the diffusion process [14,15]. Ideally, the reduction of particle
size and increasing of diffusion rate through (through increasing
the density of the particle) can reduce the temperature at which the
reactions are likely to take place significantly, even if they are not
likely to take place at room temperature.
There are two reaction kinetics reaction that is likely to take
place, and this depends on the condition of the milling used. The
first reaction is a gradual transformation, which occurs when the
reaction extends to a very small percentage after the collision. The
second form of reaction is the self-combustion reactions, which
occurs when the adequate reaction enthalpy. The second form of
reaction requires a critical milling time to be reached in order for
the reaction to start. When the temperature in the vial is recorded
during the milling process, the temperature is found to increase
gradually up to the certain point when it increases abruptly. This
increase of the temperature abruptly signifies the ignition, which
initiate the combustion process has started. After the ignition, the
temperature in the mill relatively decreases slowly. The tempera-
ture at which the temperature increases abruptly is recognized as
the ignition temperature abbreviated as Tig. Determination of this
temperature is very important while differentiating between the
structural and chemical evolution in metal alloying process [16].
Research has shown that milling achieves only particle refinement
until combustion reaction occurs. It is after the combustion reaction
that the reduction reaction occurs.
Research has further shown that the large enthalpy changes
associated with chemical changes are responsible for the occur-
rence of the combustion reaction. Combustion reaction is a result of
the temperature difference between the temperature produced by
the milling process (caused by ball-to-ball or ball-to-powder col-
lisions) Tc and the ignition temperature Tig. The combustion reac-
tion only occurs when the milling temperature Tc is more than the
ignition temperature Tig.
The ignition temperature of particular reactions depends on the
enthalpy change and the microstructural parameters, including
particle size and crystal size [16]. Since metal alloying focuses on
reducing the size of the particles, the Tig reduces as the milling time
increases. On the other hand, when the milling time increases, the
Tc also increases until it reaches a steady state. The two temperature
are very important in combustion reactions. Combustion reactions
occur when the graph of Tig and that Tc intersect, a time that is also
referred to critical milling time. Critical milling time is also called
the Tig at which the combustion reaction occurs in a reduction re-
O
action. Other interpretation that occur during Tig that lead to
combustion is that intermixing of particles, particle refinements
6.6
that occur during milling. Additionally, during milling the milling
 S.O. Yilmaz, T. Teker / Journal of Alloys and Compounds 650 (2015) 741e747
Fig. 1. DTA of a) scale, b) scale-coal mixture 40 h milled and not sintered, c) coal mixture 40 h milled and sintered at 850
C, d) coal mixture 40 h milled and sintered at 900
C.
time significantly reduced because the room temperature aging
was seen to accelerate the onset of combustion significantly [16].
3.1. Apparent specific heat
Fig. 1 illustrates the apparent specific heats for coal and scale
which were calculated under Ar atmosphere at a 10
C/min rate of
heating. When scale's apparent specific heat was measured, a
number of sharp peaks were observed. The first peak occurred at
400
C as a result of the generation of hematite (Fe2O3) [16]. As
illustrated in Fig. 1a, the second peak occurred at 685
C due to the
magnetic transformation of Fe2O3 [17]. At 700
C, the weight ratio
of scale dwindled to 99.6 wt. %. It however, rose after this tem-
perature through the magnetic transformation.
As documented in the literature [18], the evolution of CO for coal
commences at a temperature of 450
C and ends at temperatures of
around 950
C. The highest rate of evolution is attained at 720
C.
On the other hand that of H2 commences at 495
C reaches the
highest rate of evolution at 785
C and ends at 1000
C. As illus-
trated in Fig. 1b, the mixture of scale and cola produces a rapid and
significant exothermic reaction which takes place at temperatures
between 450 and 580
C. This reaction is thought to be a result of
the physical and chemical changes that pertain to the coal plastic
region (i.e. the formation, vaporization and solidification of tar).
The temperature of the exothermic reaction was about 580
C and
the weight lost was 72 wt.%
As shown in Fig. 1c, the concentrations of CO and CO2 were very
low and stay constant below 400
C for the 40 h sample at 850
C
sintering. After 400
C, the concentrations rose and became
743
tremendous after 600
C. It is accurate to assume that iron oxide
was directly reduced by coal for the temperatures interval of 700
and 800
C which led to the generation of CO2 as a primary product.
There was a substantial gasification of carbon occurred when
temperature rose above 600
C, and the reduction of the gaseous
phase facilitated the reduction of iron oxide and the weight lost was
81 wt.%. The weight lost in the 900
C sintering and 40 h MM
sample was 86 wt.%.
The sample at room temperature i.e. 25
C was dominated by
the phases of Fe3O4, and FeO. In the first step Fe2O3 was reduced
leading to the formation of Fe3O4. This formation takes place at
temperatures below 530
C and ends between 620 and 670
C. The
transformation, in this study, took place at temperatures between
420 and 480
C. At temperatures between 420 and 480
C, Fe2O3
was thermally decomposed and consequently, it disappeared. In
the second step, which according to literature happens between
670 and 740
C and ends at temperatures below 870
C, Fe3O4 was
reduced leading to the formation of FeO. The transformation, in this
study, took place at temperatures between 480 and 600
C as
illustrated in Fig. 1c. During 560 and 900
C, the reduction rate was
accelerated. At 560
C, the third step commenced where FeO was
reduced leading to the formation of metallic Fe.
For the rates of these reactions to be reasonable, elevated tem-
peratures are required. The reaction kinetics of the reduction can be
immensely increased through mechanical milling. Mechanical
milling causes repeated fracturing and welding of powder particles,
which in turn, augments the contact area of the reactant powder
particles as a result of a their reduce particle size. Consequently, the
reaction carries on without the need for diffusion through the
744 S.O. Yilmaz, T. Teker / Journal of Alloys and Compounds 650 (2015) 741e747
product layer. As a result, reactions that usually need elevated level
temperatures will take place at lower temperatures in the course
MM without application of an external source of heat. Moreover,
the rate of the diffusion process is increased by the high defect
densities produced by MM. Alternatively, the reaction tempera-
tures can be considerably reduced by the particle refinement and
resultant reduction in the diffusion distances (as a result of
microstructural refinement) regardless of whether they occur at
room temperature or not.
3.2. XRD analysis
Prior to being analyzed using XRD, samples of mechanically
milled coal and scale were prepared in a furnace at temperatures
ranging between 700 and 1000
C then cooled at a cooling rate of
around 100
C/min. Fig. 2 illustrates the XRD analysis of coal-scale
mixture that is prepared at varied sintering temperatures, the time
for mechanical milling as well as the time for sintering. At tem-
peratures of 850
C, the sample was mainly comprised of metallic
Fe and small traces of FeO. Metallic Fe phase was the sole dominant
phase at temperatures of 900
C, and the crystal size of metallic iron
in sample S3 was detected as 9.8 nm.
3.3. Iron phases analysis
The changes in sintering temperature, between 700
C and
1000
C as well as the temperature for MM, and the change of time
between 40 and 60 h are illustrated in Fig. 3a. There was a decline in
Fig. 2. X-ray diffraction analysis of mixture of coal/scale at 1/3 ratio showing the effect of sintering temperature for a) 40 h milling time, b) 60 h milling time, c) effect of milling time
900
C sintering temperature, d) effect of sintering time.
the increase of metallization ratio, and when temperatures went
beyond 1000
C, a steady-state behavior was observed. In grind of
40 h, the success in the metallization ratio seems to be higher.
Fig. 3b illustrates the correlation between MM time and the
metallization ratio. A change in the metallization ratio is observed
between 30 and 60 h. As evidenced in the agglomeration of the
powder, the MM period worsens after 40 h Fig. 3c illustrates the
correlation between metallization and sinter time. At 900
C, the
rate of metallization increases with time and stable period is
observed after 2 h.
Fig. 4 shows an SEM micrograph of sample S3 showing the size
of the metallic iron particulates. The percentage of Fe after 1 h in
activation process is approximately 85 wt.%, after 2 h it rises to
93.61 wt.% and after 4 h, it rises to 97 wt.%. There was an increase in
the surface area as well as the surface energy of the large size of the
material after activation process. As a result, the rate of reaction
also augmented. Once a rigid body is subjected to a strong external
force, its internal connection weakens and the body breaks into
smaller pieces. After the body is broken into smaller pieces, some of
its surfaces re-occur. This leads to an increment of the body's sur-
face energy and a decline in its particle volume. According to Rit-
tinger, downsizing helps in increasing surface energy as well as the
surface growth [13].
3.4. Kinetic analysis
The knowledge in the kinetic analysis is very important in the
model industrial conversion process. Specifically, the kinetic
 S.O. Yilmaz, T. Teker / Journal of Alloys and Compounds 650 (2015) 741e747
Fig. 3. Effect of sintering temperature on metallization rate.
analysis helps in understanding and predicting thermal conversion
processes, which are essential for modeling industrial conversion
processing. A research conducted to understand the kinetic analysis
of a conversion process indicated that the measured heat of
Fig. 4. SEM of sample S3 showing the size of the metallic iron particulates.
745
reduction reaction was used to measure the activation energy
required to activate a thermal reduction reaction [19]. The study
first integrated the heat of reaction cumulatively on a graph to
represent the degree of reaction. In order to effectively determine
the degree of reaction, the degree was set at zero before the reac-
tion began and then set at one it was completed. After the reaction,
the kinetics of each reaction was present a function of Arrhenius,
and the model of the reaction is as follows:
da
¼ kðTÞf ðxÞ (1)
dt
Where represent time (s), T represent temperature in (K), a
represent the progress of reaction (no units) f(a) represent the
reaction model and k(T) represent the temperature dependent
rate constant, which is further described below using the
Arrhenius


E
kðTÞ ¼ Aexp  (2)
RT
In this model, a represents the frequency factor also called pre-
exponential factor denoted as (s1), E denotes the activation energy
in (J/mol) and R denotes the gas constants (8.314 J/mol K).
Activation energy used in the above formulae refers to the
energy that must be overcome in order to initiate the bond
746 S.O. Yilmaz, T. Teker / Journal of Alloys and Compounds 650 (2015) 741e747
redistribution state, which is very critical for the conversion of
reactant into products [17]. The frequency factor as indicated in
the above model refers to the number of occurrences of the
reactive situation. However, in order to calculate A (frequency
factor) and E (activation energy) there is a need to integrate
equation (1). The first order of the equation is regarded as the
right-hand side of the equation (3) and has no exact integral. Coats
and Redfern [11] evaluated and simplified expression of the
equation is as shown below:
Za ZT

dx A E
¼ expð  dT
ð1  aÞ b RT
0 0



ART 2 2RT E
lnð1  aÞ ¼ 1 exp 
bE E RT
Take the logarithm of equation (4) yields
  

lnð1  aÞ ART 2RT E ore was 20:80.
ln ¼ LN 1   (5)
T2 bE E RT
Develop a graph by plotting the left-hand side of the equation
(5) against 1/T for every reduction reaction conducted. This will
result in a straight line with a slope E/R see in (Fig. 1). The results
as observed from the graph showed that the activation energy of
40 h MM sample was 1787 J/mol and that for 60 h MM sample was
1359 J/mol.
4. Discussion
There are a number of measuring techniques that have been
used in a bid to delve into the properties of coal-scale mixtures
when the heating rates are below 10
C/min as well as to provide
a consistent comprehension of the fundamental reactions that
take place in the course of the reduction process. The conclusion
is that the reactions of coal and scale in the coal-scale mixture
system are very intricate. In addition, the transformations in the
reactions are highly contingent on the parameters of heat
transfer such as shape, sample density, size, and heating rate. It is
imperative to note that the findings provided in this work
represent a reaction mechanism for the current parameters and
conditions of heating.
The temperature range where reduction Fe2O3 occurred is be-
tween 580
C and 670
C while that of Fe3O4 was between 670
C
and 870
C. The reduction of FeO by CO, which was produced after
gasification of carbon, occurred thereafter. The reduction of iron
oxides ended at 1200
C which lead to the production of metallic
iron. The volatile in the coal very essential in the reduction of iron
ore as it provides a sufficient reductant to reduce Fe2O3 and Fe3O4.
Prior to the initialization of the combustion reaction in the latter
type of reactions, a significant amount of milling time is needed.
The temperature increase in the vial is initially slow but after a
while, it raises all of a sudden, meaning that the ignition has taken
place. Afterwards a relatively slow decrease is observed.
This study delved into the potential of coal when reducing scale.
A technological advancement that pertains to the use of coal in
metal smelting mostly focus on the minimization of CO2 emissions
during metallurgical operations, while also facilitating efficient
management and control of biomass waste. Based on the findings
of this study, 30% by weight of coal was found to be enough to
facilitate iron ore reduction to form metallic Fe. The findings of this
study are however only limited to the iron ore and biomass samples
that were selected. The reduction processes of different iron ores
may differ they may have different properties such as different
forms of hydroxyl mineral and/or different phases of metallic oxide.
In addition, there might be some impurities such as paints in the
coal from previous treatments which might impinge on the reac-
tion. They can also be impinged on agricultural wastes which are
comprised of large amounts of mineral matter as they would
further react with the compounds of iron oxide. As a result,
different biomass types, contingent on their origin, will behave
differently when being processed and should therefore be evalu-
ated independently.
(3)
5. Conclusions
Below is a summary of this study's principal findings:
(4)
1. The percentage of Fe2O3 in the initial iron ore that was reduced
to metallic Fe at temperatures between 700
C and 1000
C was
98.7%. This took place under a heating rate of 10
C/min heating
rate and Ar atmosphere. The mass ratio mixture of coal and iron
2. The reduction of Fe2O3 using CO and H2, which are products of
the devolatilisation of coal, led to the formation of Fe3O4. This
occurred at temperatures between 420
C and 480
C.
3. The H2 and CO were also used to reduce Fe3O4 which lead to the
formation of FeO. This occurred at temperatures between 480

and 740
C. A low rate of reduction was observed between 480


and 600 C but the rate spiked up between 670
and 740
C.
4. The reduction of FeO was facilitated by CO from char gasification
and occurred at temperatures between 800
and 900
C. At
temperatures between 800
and 900
C, a high rate of reduction
was observed.
5. There were three major temperature events that were observed
in the reduction reactions. The first event was exothermic while
the other two subsequent events were endothermic.
6. Nucleation rate (N) and growth rate (G) of a-iron increased with
mechanical milling time.
7. The activation energy of the reduction reaction decreased by
mechanical milling up to 40 h MM.
8. The reaction degree of the three examined thermal regions
followed the first-order kinetic mechanism.
Acknowledgments
The authors are grateful for the financial support provided by
the FUBAP/Firat University-Elazıg/Turkey (NKUBAP.00.17.KR.14.01
number Project NKUBAP/Namık Kemal University-Tekirdag /
Turkey).
References
[1] C.P. Manning, R.J. Fruehan, Emerging technologies for iron and steel making,
J. Min. Metal. Mater. Soc. 53 (2001) 20e23.
[2] M.I.R.K.O. Komatina, W. Heinrich, The sticking problem during direct reduc-
tion, Metalurgija (2004) 309e328.
[3] M.C. Abraham, A. Gosh, Kinetics of reduction of iron by carbon, Ironmak.
Steelmak. 1 (1979) 14e23.
[4] R. Cypres, C. Soudan-Moinet, Pyrolysis of coal and iron oxides mixture 2.
Reduction of iron oxides, Fuel 60 (1981) 33e39.
[5] Y.L. Ding, N.A. Warner, Kinetics and mechanism of reduction of carbon
chromite composite pellets, Ironmak. Steelmak. 24 (1997) 224e229.
[6] S.K. Dutta, A. Gosh, Study of nonisothermal reduction of iron ore-coal/char
composite pellet, Metall. Trans. B 25 (1994) 15e26.
[7] R. Haque, H.S. Ray, A. Mukherjee, Reduction of iron ore fines by coal fines in a
packed bed and fluidized bed apparatus-a comparative study, Metall. Trans. B
24 (1993) 511e520.
[8] S. Mookherjee, H.S. Ray, A. Mukherjee, Thermogravimetric studies on the
reduction of hematite ore fines by a surrounding layer of coal or char fines.
Part 1. Isothermal kinetic studies, Thermochim. Acta 95 (1985) 235e246.
 S.O. Yilmaz, T. Teker / Journal of Alloys and Compounds 650 (2015) 741e747
[9] Y.K. Rao, The kinetics of reduction of hematite by carbon, Metall. Trans. 2
(1971) 1439e1447.
[10] Q. Wang, Z. Yang, J. Tian, W. Li, J. Sun, Reduction kinetics of iron ore-coal
pellets during fast heating, Ironmak. Steelmak. 25 (1997) 443e447.
[11] A.W. Coats, J.P. Redfern, Kinetic parameters from thermogravimetric data,
Nature 201( (1964) 68e69.
[12] P.K. Weissenborn, J.G. Dunn, L.J. Warren, Quantitative thermogravimetric
analysis of hematite, goethite and kaolinite in western-australian iron-ores,
Thermochim. Acta 239 (1994) 147e156.
[13] M. Klimakow, P. Klobes, A.F. Thünemann, K. Reedman, F. Emaerling, Mecha-
nochemical synthesis of metal-organic frameworks: a fast and facile approach
toward quantitative yields and high specific surface areas, Chem. Mater. 22
(2010) 5216e5221.
[14] P. Balaz, Mechanochemistry in Nanoscience and Minerals Engineering,
747
Springer, Berlin, Heidelberg, 2008, p. 413.
[15] C. Suryanarayana, Mechanical alloying and milling, Prog. Mater. Sci. 46 (2001)
1e184.
[16] R.M. Cornell, The Iron Oxides-structure, Properties, Reactions, Occurrences
and Uses, VCH, Weinheim, 1996.
[17] V. Strezov, Department of Chemical Engineering, The University of Newcastle,
Australia, 1999. Ph. D. thesis.
[18] Gui-su Liu, Vladimir Strezov, John A. Lucas, Louis J. Wibberley, Thermal in-
vestigations of direct iron ore reduction with coal, Thermochim. Acta 410
(2004) 133e140.
[19] T. Turanyi, A.S. Tomlin, Storage of chemical kinetic information, in: F. Battin-
Leclerc, J.M. Simmie, E. Blurock (Eds.), Cleaner Combustion: Developing
Detailed Chemical Kinetic Models, Springer, London, 2013.