Ironmaking & Steelmaking

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A study on the physicochemical and thermal

characterisation of dolomite and limestone
samples for use in ironmaking and steelmaking

Osman Sivrikaya

To cite this article: Osman Sivrikaya (2017): A study on the physicochemical and thermal
characterisation of dolomite and limestone samples for use in ironmaking and steelmaking,
Ironmaking & Steelmaking, DOI: 10.1080/03019233.2017.1337264

To link to this article: http://dx.doi.org/10.1080/03019233.2017.1337264

Published online: 12 Jun 2017.

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IRONMAKING & STEELMAKING, 2017
https://doi.org/10.1080/03019233.2017.1337264

A study on the physicochemical and thermal characterisation of dolomite and

limestone samples for use in ironmaking and steelmaking
Osman Sivrikaya
Mining and Mineral Processing Engineering Department, Adana Science and Technology University, Adana, Turkey

ABSTRACT ARTICLE HISTORY

Limestone and dolostone are used in industries depending on their physicochemical characteristics. Received 14 May 2017
They can be used in construction, agricultural, environmental industries and especially in Accepted 27 May 2017
ironmaking and steelmaking as flux. Dolomite is also used in the production of refractory materials.
KEYWORDS
As the properties of products are significantly affected by physicochemical specifications of Limestone; dolomite;
limestone or dolomite, the characterisation of those materials is important. This study was initiated physicochemical
to analyse the chemical, decrepitation, and degradation properties of dolomite and limestone characterisation; calcination;
samples to determine their suitability as flux. Since the degradation indices were found different decomposition; decrepitation
for the chemically similar samples, the study was expanded to determine the reason. Complete and degradation index
physicochemical and thermal characterisation was performed via XRF, XRD, TG, FTIR, and thin
section microscopic analyses. Although two dolomite samples were mineralogically similar, thermal
behaviours were determined different. Microscopic analyses results showed that the crystal
structures/sizes affect the thermal behaviour and degradation index of carbonate samples.

Introduction
Limestones are calcareous sedimentary rocks composed
largely of carbonate minerals such as calcite and aragonite,
which are theoretically composed of calcium carbonate
(CaCO3). The ore is widely available all over the world and
Turkey. If limestone contains a certain amount of magnesium,
it is called dolomite or dolomitic limestone. Dolomite is an
anhydrous carbonate mineral composed of calcium mag-
nesium carbonate; ideally its chemical formula is CaMg(CO3)2.
Dolomite is formed by the dolomitisation process of lime-
stones. Pure dolomite theoretically contains 30.41% CaO,
21.86% MgO and 47.73% CO2 or on a carbonate basis, it con-
tains 54.35% CaCO3 and 45.65% MgCO3. Dolomite is found
with some impurities in the Earth’s crust. Therefore, minerals
containing more than 40% MgCO3 are usually named as dolo-
mite mineral. If MgCO3 is less than 40%, they cannot be
named as dolomite; however, if they contain 20–40%
MgCO3, they can be named as dolomitic limestones. Some
impurities such as SiO2, Al2O3, Fe, S and some trace elements
can be found in the matrix of these minerals.
Depending on the quality of limestones, dolomites or dolo-
mitic limestones, they can be used as run-of-mine or processed
into a wide variety of products for different industries. They are
the raw materials for a large variety of construction, concrete,
cement [1] agricultural, environmental [2], iron and steelmak-
ing [3–6] and other industrial materials and uses. Detailed
usages of limestone and dolomite are explained elsewhere
[7,8]. For instance, a popular usage is environmental appli-
cation. Gaseous sulphur emissions from coal burning industries
such as power plants or fluidised bed combustion plants cause
acid rains. Gaseous sulphur emissions are captured by injection
of calcium or magnesium oxide sorbents in those plants [9–15].
The application of calcium-based sorbents (calcitic and dolo-
mitic) at those plants has proved to be very effective, especially
considering their lower costs [15]. The other industrial usage
fields of limestone, dolomite and dolomitic limestone are sum-
marised in Figure 1.
As a source of magnesium oxide, dolomite is used in a
variety of industries based on its physical and chemical proper-
ties. Based on physical properties dolomite is used as aggre-
gates in roads, railways and concrete production. However,
the chemical uses for dolomite are wider and more pro-
nounced. For instance, it is used in agriculture as an additive
in fertiliser and soil remediation [16,17]. Dolomite and dolomi-
tic limestone are mixed in soils and added to soilless mixtures
in floriculture as a pH buffer material and as a magnesium
source. They are also used in brick, cement, dolomitic lime,
glass, soda, ceramic industries. Moreover, they are good filler
and bleaching raw materials in paint and chemical industries.
They can be used as filtrate material and also in ferrosilicon pro-
duction. Recently they are used in landscape applications.
Dolomite is used as a fluxing agent in metallurgical, glass
and ceramic industries. The most important usage area is
the iron and steel industry [3–6]. In the iron and steel pro-
duction operations in the integrated iron and steel facilities,
dolomite, like limestone and lime, can be used to remove
impurities either in the iron ore reduction phase or in the
steel manufacturing phase. It is a good flux material as it facili-
tates the formation of slag and removes impurities such as
acidic components and sulphur from hot metal. Dolomite is
also used as fettling material (heat-resistive refractory
material) to line the interior of the open hearth or other fur-
naces for the production of steel [18]. Dolomite is also used
to make magnesium metal.
This study was initiated to analyse the chemical, decrepita-
tion and degradation properties of carbonate samples (dolo-
mite and limestone) to determine their suitability as flux
materials in iron and steelmaking. Decrepitation and degra-
dation indices were determined according to IS 10345/
10346 standards. Since the degradation indices were

CONTACT Osman Sivrikaya osmansivrikaya@gmail.com

© 2017 Institute of Materials, Minerals and Mining
2 O. SIVRIKAYA
Figure 1. Industrial usage fields of limestone, dolomite and dolomitic limestone.
determined different for the chemically similar dolomite
samples, the study was expanded to determine the reason
for the difference. Afterward, a complete physicochemical
and thermal characterisation of carbonate samples were per-
formed via XRF, XRD, TG, FTIR and thin section microscopic
analysis methods.
Materials and methods
Materials
A r.o.m. dolomite head sample (D1) was taken from a local
ore deposit in the Mediterranean Region of Turkey. In the
field, a mining company operates to produce dolomite
and limestone. Dolomite and limestone are sized into
different commercial products in the size range of 0–1, 1–
10, 20–60, and 22–60 mm by that company. Dolomite
samples (D2–D5) from sized dolomite stockpiles and a lime-
stone sample (L1) from 22–60 mm limestone stockpile were
taken. The head sample was crushed with laboratory scale
jaw crusher. The crushed sample was divided into sub-
samples using a riffle splitter. One of the representative
samples was used for screen analysis and fractions (D6–D13)
were obtained. Properties of those samples are shown in
Table 1.
Methods and equipment
Laboratory sieves, sieve shaker and a sensitive balance were
used for screen analysis. Laboratory oven was used for
drying the samples at 378 K (105°C) overnight. A laboratory
box furnace was used for the determination of loss on ignition
(LOI) of samples at 1273 K (1000°C). The box furnace was also
used for the calcination tests to determine the decrepitation
and degradation indices of the samples. A mechanical labora-
tory mortar was used to grind the samples to 100% passing
Table 1. Sample codes and their properties.
Sample
codes Type Remarks
D1 Dolomite Representative r.o.m. dolomite sample
D2 Industrially sized dolomite samples taken
D3 from commercial stockpiles
D4
D5
D6–D13 Fractions of laboratory screen analysis
L1 Limestone Industrially sized limestone product
75 μm for specific gravity, density and characterisation ana-
lyses. Specific gravities and densities of samples were deter-
mined applying water pycnometer method and using a
Micromeritics AccuPyc II 1340 model helium pycnometer
instrument, respectively.
Dry samples were kept in desiccators prior to their charac-
terisation via XRF, XRD, FTIR, and TG methods. Chemical ana-
lyses were determined with Rigaku brand Primus ZSX model
XRF spectrometer. Mineralogical analyses were carried out
with Rigaku brand MiniFlex 600 model XRD and Perkin
Elmer brand Spectrum Two model FTIR instruments.
Thermal behaviours of samples were determined using a
Hitachi brand STA7300 model simultaneous TGA/DTA
device. Thin sections were prepared from selected suitable
coarse sample pieces and examined using a Leica brand
DM750P model polarising microscope.
Decrepitation and degradation indices and
determination procedure
Decrepitation and degradation indices are properties of car-
bonate samples that should be determined prior to use in
thermal applications. Decrepitation refers to the cracking or
breaking-up of lumps of limestone/dolomite during their
descent from the top of the hot burden down into the fur-
naces. It is caused by thermal shock and differential thermal
expansion [8,19]. The mechanical resistance of limestone or
dolomite should be adequate to withstand the physical
forces and thermal shocks to which they are exposed in the
blast furnace [8]. In addition, degradation after decrepitation,
caused by movement of lump ores in blast furnaces, could sig-
nificantly change the relative particle size and their slag-
forming characteristics.
Therefore, decrepitation and degradation indices of the
limestone and dolomite samples were determined as
explained in IS10345/IS10346 standards. A sketch of the
experiment setup applied in the current study is given in
Figure 2. A plastic tube with proper diameter was used to
Particle size,
drop the samples onto a steel plate. The procedural steps
mm
for determination of decrepitation and degradation indices
r.o.m.
0–1 are given below.
1–10
20–60
(i) Limestone or dolomite sample was crushed and the 25–
22–60
Varied 30 mm size fraction was selected.
(see Table 4) (ii) About 3 kg sample was calcined in a furnace which had
22–60
already attained a temperature of 1273 K (1000°C). The
 IRONMAKING & STEELMAKING 3

Figure 2. The sketch of the experiment setup to determine the decrepitation and degradation indices of limestone or dolomite samples.

sample was kept in the furnace for two and half hours.
The calcined sample thus obtained was cooled,
weighed and then screened on a laboratory vibrating
screen. The <10 mm fraction obtained was weighed.
The percentage of <10 mm fraction with respect to the
total mass of the calcined sample screened was called
the decrepitation index.
(iii) 2 kg of >10 mm calcined sample was taken after screen-
ing. The sample was dropped twice from a height of 2 m
onto a steel plate. This material was screened at 10 mm.
The proportion of <10 mm fraction expressed as percen-
tage with respect to the initial weight was called the
degradation index.
(iv) The desirable limits for decrepitation and degradation
indices as determined above should be 10%
maximum, in order for each sample to be used in iron-
making and steelmaking [20,21].
Results and discussion
Moisture, density and specific gravity of samples
Samples were separately dried at 378 K (105°C) overnight to
determine their moisture content and to be used in density
and specific gravity measurements. The particle size of
samples used for water and helium pycnometer analyses
was 100% passing 75 µm. Tapped and loose bulk densities
of D1, D2, D3, D4, D5 and L1 samples were determined at
their particle size ranges. Moisture contents, densities and
specific gravities of the samples are presented in Table 2.
Specific gravities and densities of the samples were found to
be very similar when −75 µm samples were used in both water
and helium pycnometers. The densities were determined to be
2.84 and 2.68, which are approximate to the reported and calcu-
lated densities of pure dolomite and limestone minerals,
respectively, in literature. The loose and tapped bulk densities
were determined between 1.18 and 1.85 t m−3 as shown in
Table 2. D4, D5 and L1 had lower bulk densities than the
other samples since they had narrower particle size distributions.
Chemical analyses of samples
Chemical, loss on ignition (LOI) and total acid insoluble (TAI)
analyses were done using the dry-ground D1, D2, D3, D4,
D5, and L1 samples. LOI analyses were performed in a box
furnace at 1273 K (1000°C). TAI values were determined
using a 6 N HCl acid medium as solvent. The results of chemi-
cal, LOI and TAI analyses are shown in Table 3.
It is well known that pure dolomite contains high MgO
content with low TAI and alkali contents, and pure limestone
contains high CaO content with low MgO, TAI and alkali con-
tents. All the dolomite samples had over 20% MgO contents
with over 30–31% CaO contents. The concentrations of com-
pounds considered as impurity (TAI and alkali contents) were
found at very low levels for all the samples. For instance, TAI
contents of all the dolomite samples were approximately
0.5%. Only the limestone sample had 1.07% TAI. Therefore,
the tested dolomite and limestone samples can be classified
as chemically pure due to high MgO and CaO contents
together with low impurity contents.
Particle size distribution and chemical analyses of
fractions
One of the representative samples taken from the dolomite
head sample (D1) was crushed and a screen analysis was

Table 2. The results of moisture, density and specific gravity of samples.

Sample codes
D1 D2 D3 D4 D5 L1
Sample size (mm) r.o.m. 0–1 1–10 20–60 22–60 22–60
Moisture (%) 1.25 5.41 2.01 0.40 0.36 0.54
Loose bulk density at size ranges (t m−3) nd* 1.57 ± 0.035 1.62 ± 0.021 1.18 ± 0.022 1.23 ± 0.032 1.22 ± 0.018
Tapped bulk density at size ranges (t m−3) nd 1.83 ± 0.028 1.85 ± 0.033 1.35 ± 0.024 1.48 ± 0.036 1.38 ± 0.016
Density with Helium pycnometer, −75 µm (t m−3) 2.85 2.84 2.83 2.86 2.84 2.69
Sp. gr. with water pycnometer, −75 µm 2.84 2.82 2.81 2.85 2.81 2.67
*nd: not determined.
4 O. SIVRIKAYA

Table 3. The results of chemical, LOI and TAI analyses of samples.

Sample codes
Compound (dry wt-%) D1 D2 D3 D4 D5 L1
Sample size (mm) r.o.m. 0–1 1–10 20–60 22–60 22–60
CaO 30.11 30.79 31.23 31.09 31.36 52.019
MgO 20.55 20.46 20.44 20.48 20.25 0.577
Fe2O3 0.029 0.03 0.03 0.03 0.093 0.069
SiO2 0.153 0.19 0.12 0.14 0.065 0.342
Al2O3 0.026 0.04 0.03 0.03 0.025 0.185
Na2O 0.021 0.0124 0.0097 udl 0.022 0.0113
K2O udl* 0.004 udl 0.0027 udl 0.0395
Alkali content 0.021 0.0164 0.0097 0.0027 0.022 0.0508
TAI 0.507 0.627 0.449 0.500 0.444 1.070
LOI 47.81 46.93 46.86 46.85 46.75 44.050
*udl: under detection limit.

Table 4. The particle size distribution and chemical analyses of fractions.

Compounds (dry wt-%)
Sample codes Fractions size (mm) Fractions (dry wt-%) CaO MgO Fe2O3 SiO2 Al2O3 Na2O K2O LOI
D6 −20.0 + 9.52 2.56 31.12 20.34 0.018 0.188 0.019 udl* udl 47.05
D7 −9.52 + 6.73 24.41 30.19 20.54 0.020 0.130 0.022 0.0167 udl 47.81
D8 −6.73 + 3.36 38.38 31.33 20.24 0.016 0.054 0.019 udl udl 47.05
D9 −3.36 + 1.68 9.59 31.15 20.15 0.016 0.101 0.021 0.0185 udl 47.24
D10 −1.68 + 0.841 12.37 31.02 20.23 0.023 0.088 0.022 0.0257 udl 47.33
D11 −0.841 + 0.250 6.18 30.93 20.14 0.044 0.126 0.033 0.0154 udl 47.43
D12 −0.250 + 0.149 1.39 30.73 20.14 0.112 0.244 0.040 0.0184 0.0049 47.43
D13 −0.149 5.12 32.02 19.91 0.142 0.406 0.112 0.0131 0.0071 46.20
*udl: under detection limit.

performed. The particle size fractions were derived and results
are shown in Table 4. The chemical and LOI analyses of the
size fractions were determined. The results of chemical and
LOI analyses of the size fractions are shown in Table 4 as well.
The size fractions were chemically similar to each other. All
the fractions had over 20% MgO with over 30–31% CaO.
These results showed that if different size fractions are pro-
duced from this dolomite sample, the chemical composition
of those fractions will not be impacted. Only the finest fraction
had lower MgO and higher impurity contents than the other
fractions.
Decrepitation and degradation indices of samples
Decrepitation and degradation indices of the carbonate
samples are important specifications when they are used
in metallurgical iron and steel production. Limestone or
dolomite should be resistant to decrepitation on heating,
and should be strong enough to resist being degraded in
the blast furnace [8]. During calcination, limestone or dolo-
mite could undergo high mechanical degradation (decrepi-
tation) leading to untimely particle size reduction.
Untimely particle size reduction causes problem in blast
furnace operations. Three samples, namely D4, D5, and L1,
were suitable in terms of particle size to carry out these
tests. Therefore, decrepitation and degradation indices of
those samples were determined following the procedural
steps given under the section ‘Decrepitation and degra-
dation indices and determination procedure’. In order to
eliminate the particle size effect on decrepitation, the nar-
rowly sized particles (25–30 mm) were additionally selected
by screening for the calcination test. The results of decrepi-
tation and degradation indices of those samples are given in
Table 5.
Acceptable levels of decrepitation and degradation will be
tolerated during blast furnace operation for a problem-free
process. According to reference standards [20,21],
decrepitation and degradation indices should be lower than
10% each. The results showed that only D4 sample had
high degradation index, which was 13.15%. The other degra-
dation indices were found to be lower than the required limit.
The decrepitation indices were found to be very low, that
is, lower than 1%. These results indicated that there was no
difference in decrepitation indices; however, there was
difference in degradation indices of the tested samples.
This difference may have been caused from the differences
in chemical content, mineralogical form, thermal behaviour,
or crystalline structures of the carbonate samples. The
results of chemical analyses showed that there were no sig-
nificant differences between those samples. Since the decre-
pitation and degradation indices of the carbonate samples
were determined after thermal calcination test, the differ-
ence in those indices may be related to thermal behaviours
of the samples. Thermal behaviours may be affected by their
mineralogical and crystalline structures. Hence, the sections
‘Mineralogical analyses of sample’, ‘FTIR analyses of
samples’, ‘Thermogravimetric analysis (TGA/DTA) of
samples’, and ‘Microscopic examination of samples’ show
the results of XRD, FTIR, TG and thin section microscopic
analyses, respectively.
The chemical composition and size requirements for
limestone
According to IS10345 standard, chemical composition and
size requirements for limestone in iron and steelmaking is
given in Table 6. This table shows the required chemical com-
position and particle size of limestone for use in steelmaking
Table 5. The results of degradation and decrepitation indices of samples.
Sample code Decrepitation index (%) Degradation index (%)
D4 0.65 13.15
D5 0.32 8.46
L1 0.32 5.39
 IRONMAKING & STEELMAKING 5

Table 6. Chemical composition and size requirements for limestone according Mineralogical analyses of samples
to IS10345 standard.
Tested X-ray diffraction patterns of dry-ground samples of D2, D3, D4,
Limestone requirements limestone D5, and L1 were taken. During X-ray analyses, continuous
For steelmaking For ironmaking scanning with 0.02o step size starting with 10o and ending
Constituent (%) use use L1
90o was applied with Cu-Kα (40 kV beam energy, 15 mA
CaO 53.0, min 44.0, min 52.019
MgO 1.5, max 4.0, max 0.577 current, λ = 1.54059 Å) radiation. Only the scan range deviated
SiO2 1.5, max 6.0, max 0.0342 for the D2 sample, which was taken at 10–120°. The X-ray dif-
TAI 2.0, max 10.0, max 1.070
fraction patterns of the samples are shown in Figure 3.
Alkali content 0.2, max 0.2, max 0.0508
Size, mm 30–80 15–75 22–60 International Crystal Structure Database (ICSD) was used
Undersize or <5% <5% for identification of crystal structures of the tested samples.
oversize
Only dolomite mineral peaks (ICSD:00-036-0426) were
Decrepitation index 10.0, max 10.0, max 0.32
Degradation index 10.0, max 10.0, max 5.39 observed for the samples D2, D3, D4 and D5. The sample L1
showed only calcite mineral peaks (ICSD:01-085-1108). X-ray
patterns were in agreement with the chemical analyses data
and ironmaking in the first two columns. The last column of the tested samples.
shows the results of the tested limestone, L1. The obtained
results were compared to those required values. The L1
sample well met all the chemical requirements. The TAI and
FTIR analyses of samples
alkali contents were lower than the required specifications, The typical transmittance FTIR spectra of dolomite and calcite
indicating that the limestone had very low impurities. So minerals are shown in Figure 4 together with the FTIR spectra
the tested limestone is suitable to be used in ironmaking. of the tested D3, D4, D5 and L1 samples. FTIR spectra of the
This limestone also meets all the requirements with only 1% D3, D4 and D5 samples showed that the main absorption
low CaO content to be used in steelmaking. The L1 sample bands of dolomite at 726, 881, 1446, 1881, 2525 cm−1. L1
has suitable decrepitation and degradation indices for both sample showed main absorption bands of calcite mineral.
ironmaking and steelmaking. The absence of other absorption bands was in agreement
with the chemical and mineralogical analyses data of the
tested samples.
The chemical composition and size requirements for
dolomite
Thermogravimetric analysis (TGA/DTA) of samples
According to IS10346 standard, chemical composition and
size requirements for dolomite in iron and steelmaking is Thermogravimetric analyses are among the standard
given in Table 7. This table shows the required chemical com- characterisation methods in mineralogy. Thermal decompo-
position and size requirements of dolomite for refractory, sition of limestone and dolomite samples has been
steelmaking, ironmaking, and fettling material use in the
first four columns, respectively. The last four columns show
the results of the tested dolomite samples. The obtained
results were compared to those required values. The chemical
constituents of the tested dolomite samples completely met
the required limits. All the dolomite samples had lower impu-
rities (SiO2, TAI and alkali contents) than the required limits.
According to those results, the tested dolomite samples are
suitable to be used (i) in steelmaking, (ii) in ironmaking, (iii)
in fettling material production. The degradation index of
only D4 sample was found to be 13.15% which is higher
than the required limit (10%). Dolomite samples also met all
the requirements to be used in refractory applications with
only 0.5% low CaO + MgO content. The required particle
size can be obtained from r.o.m. dolomite, via crushing and
sizing operations. Figure 3. The X-ray diffraction patterns of D2, D3, D4, D5 and L1 samples.

Table 7. Chemical composition and size requirements for dolomite according to IS10346 standard.
Dolomite requirements Tested dolomites
Constituent (%) For refractory use For steelmaking use For ironmaking use For fettling use D1 D4 D5 D6
CaO + MgO 52.0, min 50.0, min 46.0, min 49.0, min 50.66 51.57 51.61 51.46
CaO … 30.0, min … … 30.11 31.09 31.36 31.12
MgO 20.0, min 20.0, min 19.0, min 19.0, min 20.55 20.48 20.25 20.34
SiO2 1.0, max 2.0, max … 4.0, max 0.153 0.14 0.065 0.188
TAI 2.0, max 3.0, max 8.0, max 5.0, max 0.507 0.500 0.444 nd*
Alkali content 0.2, max 0.2, max 0.2, max 0.2, max 0.021 0.0027 0.022 udlx
Decrepitation index 10, max 10, max 10, max 10, max nd 0.65 0.32 nd
Degradation index 10, max 10, max 10, max 10, max nd 13.15 8,46 nd
Size, mm Undersize 8–20 8–20 6–60 5–20 r.o.m. 20–60 22–60 9.5–20
or oversize <5% <5% <5% <5%
*nd: not determined; xudl: under detection limit.
6 O. SIVRIKAYA
Figure 4. The FTIR spectra of D3, D4, D5 and L1 samples.
investigated by researchers [22–30] but the decomposition
mechanisms of dolomite still remains obscure. Some
authors suppose the solid solutions of carbonates are
formed during decomposition, others assume primary dis-
sociation into separate carbonates or into oxides of mag-
nesium and calcium. In any case, thermal decomposition
takes place in two stages; (I) and (II) which has been gen-
erally established as [27]:
Stage (I) : MgCa(CO3 )2
MgO + CaCO3 + CO2
Stage (II) : CaCO3
CaO + CO2
The thermal decomposition of dolomite shows peculiar
characteristics depending on the atmosphere in which the
experiment is carried out. In an atmosphere of CO2 the
decomposition occurs via a two-stage process. This is
peculiar to dolomite and can be used in the identification
of dolomite in samples of unknown composition. The
same decomposition process occurs in a single stage in
an inert atmosphere of nitrogen. The partial pressure of
CO2 causes the decomposition to split into a two-stage
process [29].
Gunasekaran and Anbalagan [28] studied thermal
decomposition of natural dolomite and found two endother-
mic peaks at 1051 K (777.8°C) and 1107 K (834°C) by differen-
tial thermal analysis (DTA). The two peaks are essentially due
to de-carbonization of dolomite and calcite, respectively.
TGA and DTA were performed on each sample to under-
stand the thermal behaviour of samples under gradual
heating from room temperature to 1373 K (1100°C) with a
constant heating rate of 10 K min−1 (10°C min−1). All the
samples were ground to powder form, at similar grinding con-
ditions, to get similar particle size range to eliminate particle
size effects during TG tests. Two alumina crucibles were
used: one as reference, the other one for the test sample.
After first two tests, it was seen that the decomposition was
completed at lower than 1173 K (900°C); therefore, for the
remaining three tests, 1223 K (950°C) was selected as the
maximum temperature. Thermal tests were carried out in
normal atmosphere and also with 70cc min−1 nitrogen gas
atmosphere. Experiments were performed twice for
repeatability. The TG/DTA curves of samples are presented
in Figure 5.
The actual atmosphere around the calcining sample influ-
ences the decomposition behaviour as explained above.
However, very similar curves were obtained in the two atmos-
pheres (in normal atmosphere and with nitrogen atmosphere)
for dolomite samples D2, D3, D4 and D5, since the amount of
the test sample was very low and the resulting CO2 concen-
tration within the releasing gas was very low. Thus MgCO3
and CaCO3 decomposed as parallel reactions (single-stage
reaction). Nevertheless, in higher CO2 gas atmosphere in
industrial operational conditions the decomposition mechan-
ism changes into a two-stage reaction where MgCO3 decom-
poses first, then CaCO3 decomposes. For L1 sample, typical
thermal curves were obtained as similar to ones given in
the literature.
The thermal peaks of those tested samples were found to
be similar with each other in terms of the onset and offset
temperatures of decomposition. Decomposition tempera-
tures of the samples are given in Table 8. Residue values of
the samples obtained from both TG data and from LOI data
are also presented in Table 8 for comparison.
The initial weight losses began at about slightly over 703 K
(430°C) and then intensified at about 913 K (640°C) and com-
pleted at slightly over 1113 K (840°C). As shown in Figure 5
and Table 8, the mass losses for D4 and D5 samples initiated
at lower temperatures compared to D2, D3, and L1 samples.
Therefore, the decomposition process started sooner for D4
and D5 samples than D2, D3, and L1 samples. The limestone
sample had higher onset and offset temperatures than dolo-
mite samples. The residue values of the samples from TG data
were found to confirm the residue values of LOI test in the lab-
oratory box furnace.
The differences in degradation indices of the samples D4,
D5 and L1 may be correlated with their thermal behaviour
differences. The fastest decomposition rate and highest
degradation index occurred for D4 sample. The slowest
decomposition rate and lowest degradation index occurred
for L1 sample. Therefore, it may here be concluded that
there is a relation between decomposition rate/behaviour
and degradation index of carbonate samples. The crystalline
 IRONMAKING & STEELMAKING 7

Figure 5. The TG/DTA curves of samples with 70 cc min−1 nitrogen gas atmosphere.

structure of the samples may also affect the thermal behav-
iour and degradation characteristic of carbonate samples.
Therefore, thin section microscopic examinations of those
samples were performed.
Microscopic examination of samples
In order to examine the microscopic structures of the D4 and
D5 samples, thin sections were prepared and analysed using a
polarising microscope. Four selected examples of the thin
section photos, D4-A, D4-B and D5-A, D5-B are shown in
Figure 6.
In the thin section photos, dolomite and calcite crystals can
be clearly seen. The dark-coloured crystals are dolomite and
light-coloured crystals are calcite. There are distinct differ-
ences in the crystal sizes of the samples. The crystals of D4
sample are larger than those of D5 sample. It was reported
that, decrepitation with larger crystals is more than with
smaller ones, by McCauley and Johnson [23]. Therefore, it
can be concluded that the carbonate minerals with larger
crystal size decompose more than those of with smaller
crystal size minerals during thermal processes. Hence the
degradation index of those larger crystal size carbonate min-
erals will be greater when compared to carbonate minerals
with smaller crystal sizes. The crystal size of the carbonate
minerals may be an indicator to estimate their thermal behav-
iour during calcination reactions and degradation index. Car-
bonate samples should be selected from micro-crystalline
mineral deposits instead of those containing large crystallites
since micro-crystalline carbonates are less prone to decrepita-
tion and degradation. In addition, blending of those two types
of carbonate minerals will be a possible solution to get satis-
factory degradation index.
Conclusions
Limestone and dolomite samples were characterised via XRF,
XRD, FTIR, TG and thin section microscopic analysis methods,

Table 8. Decomposition temperatures in K (°C) of the tested samples.

Decomposition Residue values from
Sample Initial decomposition temperature, peak temperature, Final decomposition temperature, Residue values from TG LOI
code K (°C) K (°C) K (°C) data, % data, %
D2 777 (504) 1050 (777) 1111 (838) 52.40 53.07
D3 804 (531) 1062 (789) 1113 (840) 51.56 53.14
D4 704 (431) 1044 (771) 1128 (855) 52.07 53.15
D5 711(438) 1038 (765) 1115 (842) 52.76 53.25
L1 887 (614) 1070 (797) 1121 (848) 55.58 55.95
8 O. SIVRIKAYA
Figure 6. The thin section photos of sample D4 and D5. The dark-coloured crystals are dolomite and light-coloured crystals are calcite.
decrepitation and degradation indices were determined.
Briefly the tested carbonate minerals are within the specifica-
tions to be used in ironmaking and steelmaking. Following are
the results of the present study.
(i) Limestone and dolomite samples were almost pure due
to high CaO (in limestone) and MgO (in dolomites) with
lower TAI and alkali contents.
(ii) X-ray patterns were in agreement with the chemical
analyses data of the tested samples. Only dolomite
mineral peaks and calcite mineral peaks were observed.
(iii) FTIR spectra of dolomite samples showed that the main
absorption bands of dolomite are at 726, 881, 1446,
1881, 2525 cm−1. The limestone sample showed that
the main absorption bands of calcite mineral.
(iv) The tested limestone was suitable to be used in ironmak-
ing. The limestone also met all the requirements with
only 1% low CaO content to be used in steelmaking.
(v) The tested dolomites were suitable to be used (i) in
steelmaking, (ii) in ironmaking, (iii) in fettling material
production. Dolomite samples also met all the require-
ments to be used (iv) in refractory applications with
only 0.5% low CaO + MgO content.
(vi) The required particle size can be obtained from r.o.m.
dolomite via crushing and sizing by this means the
chemical contents will not be impacted and required
specifications will be obtained.
(vii) Limestone and dolomite samples met the decrepitation
and degradation indices limit; however, degradation
indices were determined different for the chemically
and mineralogically similar dolomite samples.
(viii) The reason of the different degradation indices of dolo-
mite samples was found to be related to their different
thermal behaviours. The dolomite sample to decom-
pose fastest had the highest degradation index. There-
fore, it may be concluded that there is a relation
between decomposition rate and degradation index
of carbonate minerals.
(ix) It was determined that the reason for the different
thermal behaviours is related to crystal structures.
Thin section results showed that there are distinct
differences in the crystal sizes of the samples. It can
be concluded that, the carbonate minerals with larger
crystal size decompose more than those of with
smaller crystal size during calcination. Hence the degra-
dation index of those large crystal size carbonate
samples will be greater when compared to small
crystal size carbonate samples.
Disclosure statement
No potential conflict of interest was reported by the authors.
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