Case Studies in Construction Materials 11 (2019) e00254

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Case Studies in Construction Materials

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Evaluation of chemical, mineralogical and clinker burnability properties of mudstones as cement raw
materials

A R T I C L E I N F O A B S T R A C T

Article history: The Turkish cement sector aims to contribute to sustainability by considering economic,
Received 29 September 2018 social and environmental conditions and by using technological facilities. It is very difficult
to create a sustainable economic development in an environment where resources are
becoming more and more diminishing and expensive, while preserving environmental
Keywords: resources. In the cement sector, where energy and raw materials are used heavily, replacing
Cement fossil fuels and natural raw materials with alternatives has become one of the most
Mudstone
important issues in the cement sector in recent times. In this process; primary fossil fuels
Claystone
Clinker
such as coal, petroleum coke, lignite and natural raw materials such as limestone, marl and
Alternative raw material clay have been used extensively to solve the problem of sustainable raw materials in mining
and to accelerate the search for alternative and new raw materials. For this purpose, as an
alternative to cement clay, the use of mudstone as a raw material in the cement industry
has been investigated.
© 2019 The Author. Published by Elsevier Ltd. This is an open access article under the CC BY-
NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

Since the cement industry requires high investment capital, high quality (tenor) and reserves are needed to start the
necessary investment in the sector. The chemical properties of the ore beds used in cement production, as well as their
chemical properties, closeness to the plant, their removability, fragility, grindability and burnability, low moisture content
and homogeneity are the most important factors affecting the production cost. In addition, the use of alternative raw
materials can further enhance the existing mine life and mineral quality. The realization of high quality targets placed on
cement in large quantities with a high potential for substitution and future cement depends on the availability of alternative
raw materials or industrial by products. Turkey stone, cement and ceramics industry, depending on the demand for primary
and secondary raw materials, is expected to increase until 2030, raw material requirements [1]. The raw materials required
for cement production are limestone, clay and iron ore. In addition, some gypsum is added to the cement. All these materials
are supplied from mines. Energy and fuel are consumed during production and transportation. Another important issue is
the rapid depletion of resources. In addition to cement raw materials for the reduction of natural resources; sludge, gypsum,
gypsum waste, bleaching waste, sludge waste, casting sand, iron dust, tufal, gypsum, fly ash, iron slag and excavation soil
sludge land etc. materials are used as an alternative to cement raw materials. These alternative raw materials are added to
the raw mixture of cement at a certain rate to form the composition of the cement [2].

2. Literature Screen

2.1. General description of mudstone

Mudstone is a fine-grained, degradable sedimentary rock composed of clay and mud. Shales, also called mudstone or
claystone, were formed millions of years ago by the deposition and accumulation of very small clay particles that broke off from
an old rock mass that had been eroded by rainwater and rivers. Over time, the deposits on the bottom of the new deposits
accumulated on top of the pressure has become a solid rock. The density of the sludge ore in the land is assumed to be 2.0 g / cm3

https://doi.org/10.1016/j.cscm.2019.e00254
2214-5095/© 2019 The Author. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).
2 / Case Studies in Construction Materials 11 (2019) e00254

on average. Since the clay mineralization is in a hard structure, production can be carried out by performing drilling-blasting and
size reduction processes in stages during the production activities by using open operation method in quarries [3].
In the study area, the thickness of the mudstone ore is around 60 m on average. The reserve amount was set at
approximately 11.987.760 tonnes considering the field work and the area planned to be studied with ore propagation [3].
The mudstone consists mostly of shafts (4–62 microns) and clay (4 microns) in size. Claystone is generally very fine-
grained and homogeneous, separated from the shaft stone (siltstone). Shales are characterized by the ability to separate the
leaves along stratigrafi parallel to the bedding. Many shales are laminal. The mud stones do not show lamination, and when
broken, the crust is broken and massive. Marn is a limy mud stone [3].

2.2. General geolgy of mud stone

The formation consists of red-burgundy micritic limestone and limestone mudstone alternations. Inözü _ anticline and
Kavak County, located in the NW section of the study area, are located on the wings of anticlines and synclines between Sarı
alan and Belalan villages (Fig. 1). The formation is a typical example of the Kapikaya Summit. The unit is a thin-medium

Fig. 1. General geological map of the site (Samsun/Kavak).

 / Case Studies in Construction Materials 11 (2019) e00254 3

bedded red-burgundy biomicrit and pelagic limy mudstone alternation. Within the limestones, pink-beige colored chert
ovules and thin-bedded volcanic intermediate bands are seen. The thickness varies between 53–106 m. The Kapan Throat
formation was identified as Santonian-Campanian based on the Globotruncana fauna. The formation was precipitated in a
calm and deep sea environment [4].

2.3. Cement production methods

Portland cement is the basic ingredient of concrete. Concrete is formed when portland cement creates a paste with water
that binds with sand and rock to harden. Cement is manufactured through a closely controlled chemical combination of
calcium, silicon, aluminum, iron and other ingredients [5].
Common materials used to manufacture cement include limestone, shells, and chalk or marl combined with shale, clay,
slate, blast furnace slag, silica sand, and iron ore. These ingredients, when heated at high temperatures form a rock-like
substance that is ground into the fine powder that we commonly think of as cement [5].
Cement plant laboratories check each step in the manufacture of portland cement by frequent chemical and physical
tests. The labs also analyze and test the finished product to ensure that it complies with all industry specifications.
The most common way to manufacture portland cement is through a dry method. The first step is to quarry the principal
raw materials, mainly limestone, clay, and other materials. After quarrying the rock is crushed. This involves several stages.
The first crushing reduces the rock to a maximum size of about 6 in. The rock then goes to secondary crushers or hammer
mills for reduction to about 3 in. or smaller [5–7].
The crushed rock is combined with other ingredients such as iron ore or fly ash and ground, mixed, and fed to a cement
kiln.
The cement kiln heats all the ingredients to about 2700 degrees Fahrenheit in huge cylindrical steel rotary kilns lined with
special firebrick. Kilns are frequently as much as 12 feet in diameter large. The large kilns are mounted with the axis inclined
slightly from the horizontal.
The finely ground raw material or the slurry is fed into the higher end. At the lower end is a roaring blast of flame,
produced by precisely controlled burning of powdered coal, oil, alternative fuels, or gas under forced draft.
As the material moves through the kiln, certain elements are driven off in the form of gases. The remaining elements unite
to form a new substance called clinker. Clinker comes out of the kiln as grey balls, about the size of marbles [5–7].
Clinker is discharged red-hot from the lower end of the kiln and generally is brought down to handling temperature in
various types of coolers. The heated air from the coolers is returned to the kilns, a process that saves fuel and increases
burning efficiency.
After the clinker is cooled, cement plants grind it and mix it with small amounts of gypsum and limestone. The cement is
now ready for transport to ready-mix concrete companies to be used in a variety of construction projects [8] (Fig. 2).

Fig. 2. Cement production flow chart [7].

4 / Case Studies in Construction Materials 11 (2019) e00254

3. Materials and methods

3.1. Materials used in experimental studies

In this study, the mudstone, limestone and clay obtained from The Black Sea region (Samsun, Turkey) were used. The iron
ore used in the study was obtained from Malatya Hekimhan quarries. Chemical analysis of the iron ore used in the
experiments has been used as a corrective additive substance in the raw meal compositions.The chemical compositions of
the mudstone, limestone, clay and iron ore (Table 1) were evaluated by usingX-ray fluorescence techniques and ICP/ES and
MS(ACMEAnal. Lab.). As can be seen in Table 1, mudstone sample contained significant levels of CaCO3 (32.26%) and SiO2
(30.45%). According to the XRF results, the lime saturation factor (LSF), silicate modules and aluminum modules of the
cement main raw materials were calculated using the Bogue formula. Loss on ignition analysis is performed for each raw
material and the results are given in Table 1 (TS EN 196-2, [11]). Particle size distribution of the as-received sample using
laser diffraction method (Malvern Master Sizer) was determined to be 80% of the sample finer than 80 m. Mudstone has a red
color and massive appearance and its specific gravity was 2850 kg/m3. The crystalline phase composition of the material was
investigated using X-ray diffractometer (XRD, RIGAKU, D/Max-IIIC). The XRD pattern shown in Fig. 4 revealed the presence of
CaCO3, Al2O3, Fe2O3 and SiO2 in the sample.

3.2. X-ray spectrometry (XRF) sample preparation and analysis

Chemical analyzes of cement samples formed by adding cement clinker and gypsum were determined by XRF method.
The weighed 0.6 g of milled sample was placed into 0.03 g of lithium iodide and 4.6 g of dilithium tetraborate platinum
crucible. A spatula was mixed with the material in a crucible to form a homogeneous mixture. The homogenous material
in the crucible prepared for the melter is placed in tablet mold. The four-stage melter operates in the first 10 min of
heating, 5 min of melting, last 5 min of cooling and unloading programs. The glass tablets formed in the melting device
were read in X-ray fluorescence spectrometer and the chemical content results were recorded on the computer (TS EN
196-2, [11]).

3.3. Physical and mechanical tests for the clinker products

Portland cement samples representative of clinker products were produced by fine inter-grinding the clinker samples
with gypsum (4%) in a laboratory mill. The chemical composition of the natural gypsum used in the experiments is also
presented in Table 7. The cement samples obtained were then subjected to the physical characterization prior to the
mechanical tests using the procedures outlined in TS EN 196-1,3,6 [15,16]. The cement products were used to
preparemortar test specimens (three specimens for each test) with dimensions of 40 mm
40 mm
160 mm for
mechanical tests. Cement (450 g), sand (1350 g) andwater (225 ml) waswell-mixed in Seger mortar mixer and the
mixturewas put into the molds. The mortar samples were then allowed to cure under suitable conditions and tested for
compressive strength at 2-, 7- and 28-day curing periods. The mean values obtained from three replicate specimens were
presented in the results.
The weight loss of a cement sample with a known weight (1  0.05 g) at the very high temperature (975  025  C) is called
“Loss on Ignition " and this value is expressed as% (Kaya, 2010). The following steps were followed in this test. The crucible
with fixed weighing was taken 1.00 g (m1) from the dewatered cement sample with a sensitivity of 0.0001. 975  C  25  C for

Table 1
Chemical properties of the cement raw materials.

Content Mud stone Clay Limestone Iron ore Bauxite ore

% % % % %
SiO2 30,45 58,83 0,24 20,51 19,1
Al2O3 4,68 16,44 0,07 4,14 45,4
Fe2O3 2,3 7,58 0,05 64,58 18,18
CaO 32,26 1,01 55,45 0,71 1,68
MgO 0,52 3,08 0,49 0,65 0,31
SO3 0,07 0,17 < 0,01 0,58 0,3
Na2O 0,03 1,3 < 0,01 0,02 1,02
K2O 1 3,46 0 0,05 1,01
TiO2 0 0,65 0 0 0
P2 O 5 0 0,12 0 0,23 0,02
Cr2O3 0 0,03 0 0 0
Mn2O3 0 0,09 0 0,27 0
Loi 28,49 6,84 43,68 7,69 7,4
Total 99,8 99,6 99,98 99,43 99,96
_
SIM 4,36 2,44 2 – –
ALM 2,03 2,16 1,4 – –
 / Case Studies in Construction Materials 11 (2019) e00254 5

15 min in the furnece. The desiccator is cooled to room temperature and weighed. It was reheated for 5 min, cooled to room
temperature and weighed again. This process was continued until reaching the fixed weight (m2) (TS EN 196-2, [11]).
Calculation:
 
m1 m2
Loi ¼
1000 ð2:1Þ
m1

m1: Mass of test sample (g) m2: The mass of the heated test sample after constant hardness (g)

3.4. Raw mix preparation

The following parameters were constant in all the mixes and they were adjusted according to Eqs. (1)–(3):
SiO2
Silikat Mod ul u ðS_ IMÞ ¼ ð1Þ
Al2O3þFe2O3

Al2O3
Al uminyum Mod ul u ðALMÞ ¼ ð2Þ
Fe2O3

CaO
LSF ¼ x100 ¼ 98% ð3Þ
2; 8SiO2þ1; 18Al2O3þ0; 65Fe2O3
Materials with a high LSF content require a high amount of fuel in order to be able to be burned at high temperatures,
theraw meal seldom sinterizes, the unbaked lime ratio becomes high and catches high early strengths, but the free lime
amount causes a sudden volume expansion in the concrete, cracking the concrete mass, resulting in weaker strengths.
Burning is relatively simple for raw material compositions with a low LSF amount, but if the amount of C3S is too low and the
amount of C2S is too high, the cement strengths will be low. For a quality Portland cement mortar, LSF is expected to be
between 0.88-0.95.
The raw mixes were prepared as follows: after in a turbula for 60 min, the components were stirred in a suspension
with ethanol in an agate mortar for 30 min, not to alter the pre-established particle size distribution. The excess of
ethanol was removed by heating the mix under an infrared lamp. Tablets weighing around 4–5 g each and 3 cm in
diameter were prepared from each raw mix and then clinkerized at the following temperatures: 1270 OC, 1350 OC, 1400
O
C, 1450 OC, and 1500 OC. The samples were heated at each temperature for 30 min and then cooled at ambient
temperature.
XRD mineralogical analysis using a Philips PW 1710 diffractometer. Samples were ground to a particle size lower than
45 lm. At 2ø diffraction angles ranging from 5 to 60 using a step of 0.020.
Morphological analysis a Nikon Eclipse ME600 reflected light microscope, for which the clinker was previously
encapsulated in epoxy resin, cut and polished.

4. Results and discussion

Clay, mudstone and limestone were used in this study, which investigated whether mudstone could be used as an
alternative to clay stone in cement production. After mixing the mudstone and claystone samples obtained from the raw
material fields separately, they were turned into composite samples and a series of experimental studies were carried out on
these samples at the laboratory scale. The findings obtained within the scope of the thesis work are explained in the
following headings.
Chemical analyzes were carried out in order to determine the chemical composition of the cement mixtures and the
cement clinker obtained in the rotary furnace after the heat treatment. It is known that CaO, SiO2, Al2O3 and Fe2O3 combine
to clinker under certain process conditions.
The lack or excess of one of them prevents the clinker from being formed and fully formed. According to the type and
properties of the cement to be produced, the ratio of oxides and lime standard should be adjusted. Chemical contents of
limestone, mudstone and clay stone raw materials are suitable for the production of Portland cement (Table 1).
The chemical analysis data of limestone, clay and mudstone, which were used in preparing cement clinkers, are given in
Table 1. When mudstone and clay samples are compared, it is seen that mudstone SiO2, Al2O3 and Fe2O3 ratios are low but
CaO value is high. For this reason, it is seen that iron ore and clay minerals are required externally in order to obtain a sample
of the mudstone raw meal.

4.1. Raw meal properties of raw materials

The raw material composition and homogeneity in cement production is an important factor affecting the economy of
the production process and the quality of the cement during the usage phase. Therefore, it should be ensured that cement
6 / Case Studies in Construction Materials 11 (2019) e00254

raw materials are produced in desired chemical composition and homogenously, and these properties should be protected
during the production stages depending on the type of cement produced during the production stages. The composition
and homogeneity of the raw materials used in the production of cement is achieved by the effects of the desired type of
cements on the desired properties (resistance, freezing time, reaction time, etc.) during the production process (easy
grindability, easy cooking etc.) The raw material composition and its homogeneity are of great importance [9]. The
discontinuous particles of silica and aluminum from the limestone, which are contained in the limestone material fed from
the furnace, change the cement raw material mixing ratios. In order to make a smooth mixture of raw materials and to feed
a stable mixture of raw materials to the mill, it is very important and useful to identify these samples in XRD, especially
step-by-step or vascular vessels are screened and samples taken [10]. Using the high resolution X-rays diffractometer,
mineralogical analysis was performed for the cement limestone sample taken from the furnace. Calcite (CaCO3) mineral
was found as a result of the XRD analysis of the limestone sample used in the experiments and no other minerals were
found (Fig. 3). Siliceous structures in limestone quarry where sample is taken are found in very small amounts especially in
metamorphism and alteration of veins. In the results of chemical analysis (XRF), siliceous structures within the limestone
vessels do not exceed 5%.
The composition and homogeneity of the raw materials used in cement production are affected both by their effects
during the production process (easy grinding, easy baking, etc.), by the properties desired (strength, freezing time, curing
time etc.) during use and by obtaining the desired mineral phase ratios of the produced different types of cements [11].
When the XRD graphs of the mudstone and clay stone composite samples taken from different zones of the quarry are
examined in Fig. 4. Mainly calcite (CaCO3), quartz (SiO2), chlorite [(Mg, Al, Fe) 6 (Si, Al) 4O10 (OH) 8], albite NaAlSi3O8,
muscovite [(K, Na) Al2 (Si, Al) 4O10 (OH) 2] and montmorillonite NaO.3 (Al, Mg) 2Si4O 10 (OH) 2  8H2O minerals were
determined to contain.
Along with these minerals, the mudstone contains the orthoclase (KAlSi3O8) and the ankerite (Ca, Mg, Fe) (CO3)2, while
the clay stone contains the anorthite (CaAl2Si2O8) mineral. As a result of the evaluation of peak intensities, it can be said that
the mudstone unit has a high grade in terms of quartz, muscovite and co-citates.
As can be seen from the clay stone XRD graph in Fig. 4, it is seen that the amount of quartz in the clay stone sample is
higher than the mudstone sample.
From this, we can say that the amount of fuel required to cook the clay stone mineral will be more than mudstone, and the
grinding of the clay stone mineral will be more difficult than the mudstone. Comparative XRD graphs of mudstone and clay
stone are given in Fig. 4.
The raw material used in the production of cement must be active silicates which may react under silica cooking
conditions. The presence of silica in quartz form is never desired. Because kristal SiO4 ip crystals in quartz are in the
form of tetraer, free bonds are clamped between themselves and form a very strong crystal structure. In this case, the
ability of the quartz to enter the chemical reaction decreases as the free bonds are reduced. In order to react quartz
relatively, very fine grinding, high temperature and long cooking time are required, all of which are cost-increasing
[12,13].
According to the mineralogical claystone composition of the mudstone composition, the peak strengths of the XRD
graphs were found to be higher than that of the metaphoric composition. Besides, muscovite which has positive effects on
firing in clay stone composition and chlorite minerals were found to be less than metaphoric composition.
In laboratory scale, 6 different raw material compositions were prepared (lime saturation factor (LSF): 98) using 1 kg
mudstone, 1 kg claystone and 1 kg limestone samples (Table 2). Silicate (SIM) and aluminum modules (ALM) were
calculated using the Bogue formula of the raw material compositions. The mixture ratios of the prepared raw material

Fig. 3. Limestone XRD chart.

 / Case Studies in Construction Materials 11 (2019) e00254 7

Fig. 4. Comparative XRD graph of mudstone and clay stone.

Table 2
Raw meal mix composition (% by weight).

Codes Lime Mud stone Clay Iron ore Bauxite ore

stone stone
HK 1 52,1 46,9 0 1 1
HK 2 51,6 48,4 0 0 0
HK 3 68,5 16,5 15 0 0
HK 4 68 16,8 14,2 1 1
HK 5 54 42 0 1,5 2,5
HK 6 76,9 0 22,1 1 0

compositions are given in Table 2. Because the raw materials are high in SIM and ALM, the closest compositions to the raw
meal content have been prepared. Additional raw materials containing alumina (such as bauxite) have been added to iron
compounds (such as iron ore) and Al2O3 minus to the Fe2O3 deficiency in the main raw materials used to form the clinker
composition of the raw meal samples to be produced. The addition of Fe2O3 (Iron Ore) and Al2O3 (bauxite) to the raw
material is expected to act on the baking facilitator The LSF values were determined to be 98 when raw material
compositions were formed and cement modules were calculated according to the Bogue formula using the raw meal
chemical analysis (Table 3). The LSF value expected from a clinker in normal condition is between 95 and 98. The LSF
values above 100 indicate that there is free lime that has not reacted in the environment. For this reason, if LSF is equal to
100, all the other oxides will react with calcium oxide and the excess lime will be in free state. There is always a free lime

Table 3
Results of chemical analysis of raw meals.

Content Raw Meal I Raw Meal II Raw Meal III Raw Meal IV Raw Meal V Raw Meal VI
% % % % % %
SiO2 14,68 14,86 14,01 13,6 13,81 13,46
Al2O3 2,26 2,30 3,29 3,80 3,18 3,72
Fe2O3 1,72 1,14 1,55 1,77 2,36 2,32
CaO 44,05 44,23 43,46 43,04 43,58 42,89
MgO 0,50 0,50 0,88 1,08 0,57 1,06
SO3 0,01 0,01 0,04 0,05 0,02 0,05
Na2O 0,01 0,01 0,05 0,07 0,02 0,07
K2O 0,05 0,04 0,42 0,62 0,11 0,60
KK 36,0 36,1 36,0 36,1 33,19 35,65
Total 99,28 99,19 99,7 99,97 99,82 99,83
LSF 98,13 98,1 98,49 98,22 98,96 98,41
_
SIM 3,69 4,32 2,90 2,44 2,49 2,23
ALM 1,32 2,02 2,12 2,15 1,35 1,60
8 / Case Studies in Construction Materials 11 (2019) e00254

Table 4
Clinker chemical analysis results.

Content Clinker V Clinker VI

% %
SiO2 21,69 20,97
Al2O3 4,99 5,78
Fe2O3 3,71 3,62
CaO 68,46 66,82
MgO 0,89 1,65
SO3 0,03 0,08
Na2O 0,03 0,11
K2O 0,17 0,94
Loi 0,3 0,3
Total 100 100
SiM 2,49 2,23
ALM 1,34 1,60
LSF 99,14 98,41

Table 5
Clinker main component ratio.

Content Clinker V Clinker VI

% %
C 3S 70,83 64,48
C 2S 8,77 11,5
C 3A 6,96 9,21
C4AF 11,29 11,01
liquid phase 24,22 27,99

Fig. 5. optical microscope image a) mudstone clinker V b) clay clinker VI.

in the system that has not reacted a bit, and the LSF value is below 100. The high LSF value increases fuel consumption
because lime is a difficult element to burn, and due to this feature, the anzast (mantle inner lining protective shell)
formed in the oven is weak [14].
The silicate modulus is one of the most important parameters affecting the quality of clinker.
_ is not reduced in the
The preferred cyclic modulus value for the enterprises is between 2.3–2.45 [15]. If the amount of SIM
industrial works to be done with raw meal sample, it is predicted that the consumption power of the raw meal will be
increased and the fuel consumption of the rotary kiln will increase. At the same time, due to the high silicate modulus, a
production process can be realized in which the initial curing time of the cement to be formed may be delayed, the furnace
brick lining may weaken in the anzast region and the furnace bricks may be damaged. When SIM and ALM of the prepared
farin compositions were examined, Farin V and Farin VI samples for cement production were found to be more suitable. For
this reason, these two samples were subjected to the laboratory scale burnability test.
 / Case Studies in Construction Materials 11 (2019) e00254 9

Fig. 6. optical microscope image a) mudstone clinker V b) clay clinker VI.

Table 6
Bogue and optical microscope phase determination results of Claystone and Meta schist clinker.

Content Clay-clinker Bogue Clay-clinker Optic Mudstone clinker Bogue Mudstone clinker Optic
% % % %
Alite C3S 51,22 51,97 54,28 54,68
Belite C2S 21,37 26,09 16,55 17,31
(C3A + C4AF + Free CaO + Alkali Sulfate) 18,70 16,91 11,04 31,01

Table 7
Physical and mechanical tests results for the clinker samples.

Clinker Types S.M Al.M. LSF (sieve) (water) (Soudness) Compressive Strenght N/mm2

% 90 mik % mm 2.days 7.days 28. days

Clinker V 2,30 1,49 100,46 1,20 23,40 2 23,0 39,20 55,0
Clinker V 2,29 1,46 99,52 1,40 23,40 1 22,5 41,90 51,90
Clinker VI 2,32 1,44 99,15 1,20 23,60 1 22,0 40,60 54,10
Clinker VI 2,32 1,41 99,63 1,00 23,40 1 21,8 39,80 49,70

4.2. Burnability properties of raw materials

In preparation of the raw meal for examination of burnability; LSF: 98 based on clinker parameters at optimum quality
was taken as the basis, and depending on the material characterization, the mudstone formed raw meal was found to be SIM:
2,49 and ALM: 1,35; a mixture of farin with SIM: 2.23 and ALM: 1.60 was prepared. The prepared samples were heated at
1200-1300-1350-1400 and 1450  C in the protherm ash furnace for the burnability test. The free CaO values of the clinker V
sample in the clinker samples obtained at 1450  C of the obtained clinker samples were 1.80; the free CaO values of the
clinker VI sample were found to be 1, 50, indicating that both of the prepared powders have easy burning characteristics (less
than% S.CaO: 2.00).(Table 4)
When the clinkers formed are examined in terms of quality parameters, it is observed that both clinker samples have
higher quality than average quality (C3S > 60.0%). Clinker V shows a high (24.22%) level depending on raw material character,
low ICM and high ALM values depending on the raw material characterization of Clinker VI, low (optimum 27%) depending
on SIM and high ALM values. Klinker V shows that a high-early-strength cement can be produced with high C3S content,
whereas Klinker VI shows a high cement content with a high C2S content (Table 5).
Optical microscope images were taken from the samples taken from mudstone and clay rock clinker and shown in Fig. 5.
Alite crystals are colored brown and generally show a dense structure. (Fig. 5). The dense phase of the alite phase is due to the
fact that the raw mixture is rich in lime. The dimensions of the alite crystals of the mudstone clinker are smaller than the
dimensions of the clay stone clinker and are uniform. The fact that allite crystal shapes show a good cooking and that the
allites have a distinct shape indicate that the cooking and cooling are well done. As seen in Fig. 5, the allite structure of the
mudstone clinker is more pronounced than the clay stone clinker. This shows that the mudstone clinker is better baked than
the clay stone clinker, and the alite minerals are higher.
10 / Case Studies in Construction Materials 11 (2019) e00254

It is seen that in the clay stone samples belit mineral (blue color) is more dense and clustered than mudstone clinker. This
also indicates that the clay stone is less homogenous than the mudstone raw mixture. The dense phase of the test phase
affects grindability negatively. Belit minerals are scattered among allites in a large part of their clustered form in some
regions. This situation requires coarse grinding of coarse grained minerals in the clay stone raw mixture and for complete
homogenization.
Mudstone clinker and clay rock clinker samples were examined in detail. It was found that the liquid phase (gray part)
was fine crystallized in the mudstone clinker, the C3A and C4AF structures were visible and fine crystallized. The C3A phase
in the mudstone clinker is generally cubic in the sample and it can be said that there is a small amount of orthorhombic C3A
minerals. The fine crystallization of the liquid phase supports that the cooling is done at sufficient speed and that the crystals
are formed in the desired manner. In the clay stone clinker, the liquid phase was thicker and dispersed. The amount of free
lime found in the clay stone clinker is less common to the free lime mineral found in the metaphyseal sample (Fig. 6). This
shows that the metaphoric clinker is more easily cooked than the clay stone clinker and is a better quality clinker. In addition,
the results of free lime age analysis and mineralogical analysis carried out in the TÇMB laboratory support this (Table 6).
ompared to metal shale and clay stone and clinker formed in laboratory conditions, it is seen that the amount of C3S is
higher and the amount of C2S is lower. According to the results of the clinker phase determination, it can be said that the
clinker formed by the mudstone may be higher in quality than the clay produced by the clay stone and the strengths of the
cements to be produced may be higher (Table 6). The size of the alite crystals does not only affect the cost of
grinding (too much energy is needed to shrink large crystals), which also affects cement strength. Because of the
formation of a larger surface for hydration, it is known that the strength of the smaller alite crystal size is higher than the two
cement of the same chemical composition [16].

5. Conclusions

In this study, inwhich the samples of the raw material produced from the furnaces were separately blended, composite samples
were produced and experimental studies were carried outon laboratory scale in these samples. As a resultof the experiments, it has
been determined that in the production of cement the mudstone can be used as an alternative to clay stone and also it is more
advantageous in terms of both economic and cement quality compared to clay stone. The chemical structure of the mudstone
vessels in the quarries where the samples are provided is more homogenous than clay stone and more suitable for cement
production. Chemical analysis showed that the mudstone raw material is very rich in calcium and silica. In this respect, It has a more
stable structure than other cement raw materials. Therefore, the cement produced with clay stone requires the use of various
regulatory raw materials and thus creates additional costs. As a result of the mineralogical analysis of the clinkerization samples
obtained for the investigation of the furnace prepared by the mudstone and clay stone, it was observed that the basic clinker phase
was formed for both raw materials. 1.60 of free lime in the clinker formed in 1450 C shows that the head prepared with mudstone
has an easy cooking character. It is observed that clinker formed by cooking clay prepared with clay stone has a hard cooking
character as it has 3% or more free lime. Furthermore, the high silica content in the clay stone raw material increases the cooking
temperature of the clay stone. This means a higher amount of coal consumption in cement production. By mineralogical surveys,
the mudstone was determined to have lower quartz content than the clay stone. When it is considered that quartz content has
negative effects on production processes such as grindability, freezability and abrasion, it can be said that the reason for the more
economical and high quality of the cement production with the use of mudstone is mainly due to its mineralogical structure.

Conflict of interest

None.

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Abdul Vahap Korkmaz

Afyon Kocatepe University, Department of Industrial product design, Dinar/Afyonkarahisar, TurkeyE-mail address:
avkorkmaz@aku.edu.tr (A. Korkmaz).

Received 29 September 2018