ASSESMENT OF AVROMAN LIMESTONE FORMATION FOR PORTLAND CEMENT INDUSTRY HALABJA AREA SOUTH-EAST SULAIMANI, KURDITAN REGION NE-IRAQ.

A THESIS SUBMITTED TO THE COUNCIL OF FACULTY OF SCIENCE AND SCIENCE EDUCATION SCHOOL OF SCIENCE AT THE UNIVERSITY OF SULAIMANI IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN GEOLOGY

By Chro Muhammad Fatah Amin B.Sc. Geology (2006), University of Sulaimani

Supervised by Dr.Tola A. Mirza Mohammed Assistant Professor

October, 2014 A.D.

Galarezan, 2714 KU. 1

Sahih International

And He has cast into the earth firmly set mountains, lest it shift with you, and [made] rivers and roads, that you may be guided, (15) II

Supervisor Certification I certify that this thesis entitled "Assessment of Avroman Limestone Formation for Portland Cement industry Halabja area south-east Sulaimani, Kurdistan Region, NE-Iraq " accomplished by (Chro Muhammad Fatah Amin), was prepared under my supervision in the School of Science, Faculty of Science and Science Education at the University of Sulaimani, as partial fulfilment of the requirements for the degree of Master of Science in Geology (Industrial Rocks and Minerals).

Signature: Supervisor: Dr. Tola A.Mirza Mohammed Scientific title: Assistant Professor Date: 21 / 7 / 2014

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Certification of the Department In view of the available recommendation, I forward this thesis for debate by the examining committee.

Signature: Name: Dr. Diary A. Muhammad Scientific title: Assistant Professor Head of Geology Department Date: 21 / 7 / 2014

_________________________________________________________________________

III

Linguistic Evaluation Certification This is to certify that Dr. Bakhtiar Sabir Hama has proofread this thesis entitled “Assessment of Avroman Limestone Formation for Portland cement industry Halabja area south-east Sulaimani, Kurdistan Region NE-Iraq”, prepared by Chro Muhammad Fatah Amin.

After marking and correcting the mistakes, the thesis was handed again to the researcher to make the corrections in this last copy.

Signature: Proofreader: Dr.Bakhtiar Sabir Hama Date: 14 / 08 / 2014

Department of English, School of Languages, Faculty of Humanities, University of Sulaimani.

_________________________________________________________________________

IV

Examining Committee Certification We certify that we have read this thesis entitled " Assessment of Avroman Limestone Formation for Portland cement industry Halabja area south-east Sulaimani, Kurdistan Region NE-Iraq" prepared by (Chro Muhammad Fatah Amin), and as Examining Committee, examined the student in its content and in what is connected with it, and in our opinion it meets the basic requirements toward the degree of Master of Science in Geology (Industrial Rocks and Minerals).

Signature:

Signature:

Name: Dr. Sabah A. Ismail

Name: Dr. Ahmad M. Ahmad Aqrawi

Scientific title: Professor

Scientific title: Assistant Professor

Address: University of Kirkuk

Address: University of Salahaddin

Date: 27 / 11 / 2014

Date: 27 / 11 / 2014

(Chairman)

(Member)

Signature:

Signature:

Name: Dr. Sardar M. Ridha Babashekh

Name: Dr.Tola A. Mirza Mohammed

Scientific title: Lecturer

Scientific title: Assistant Professor

Address: University of Sulaimani

Address: University of Sulaimani

Date: 27 / 11 / 2014

Date: 27 / 11 / 2014

(Member)

(Member and Supervisor)

------------------------------------------------------------------------------------------------------------Approved by the council of the Faculty of Science and Science Education Signature: Name: Dr. Bakhtiar Q. Aziz Scientific title: Professor Dean of Faculty of science and Science Education, University of Sulaimani Date:

/

/ 2014

_________________________________________________________________________ V

Dedicated to:

Memory of my Father My Mother My Sisters & Brothers My Friends Who Taught Me a Letter in the Present Life

Chro ____________________________________________________

VI

Acknowledgments First of all I deeply thank Allah for all benefits I wish to express my deep gratitude and appreciation to my supervisor Assistant Professor Dr.Tola A. Mirza for suggesting the research project and for her continuous guidance and encouragement during my work. I am extremely thankful for her endless effort in completing and revising the thesis and providing invaluable assistance and inspired ideas. Special thanks to Professor Dr. Kamal H. Karim, Assistant Professor Dr. Ibrahim M.J. Mohiadeen, Dr. Musher M. Qadir and Dr. Sardar M. Raza, at Department of Geology University of Sulaimani who provided me with valuable comments and suggestions. I also greatly appreciate the assistance of the Mass cement Factory in the Iraqi Kurdistan Region and Mr. Adil J. Abdula (Director of quality control) at this Factory and all staff worked their particularly Miss. Dnya Sh. Muhammad and Miss. Golabakh H. Karim. My thanks also to Dr. Mazn Muhammad of Physical Department, University of Basra for his support in mineralogical analysis of insoluble residue by XRD. My best thanks to the Dean of the Faculty of Science and Science Education Dr. Bakhtiar Q. Aziz and the Head of Department of Geology Dr. Diary A. Mohammad for their generous support including equipment facilities that offered to this work. My Sincere thanks to all of the teaching staff members of the Department of Geology, University of Sulaimani for their help and support. And I would like to show my gratitude of my friends Mr. Hawber A. Karim, Mr. Asaad I. Mustafa, Mr. Zana M. Muhammad and my nephew Rebar J. Toffeq for their considerable assistance in field work. Finally, I would like to express my sincere gratitude to anyone who helped me throughout the preparation of the thesis and to my family for their encouragement, support and patience.

Chro 2014 _______________________________________________________________________________________

VII

Abstract This research involves the evaluation of limestone of Avroman Formation (U. Triassic) as Potential Raw Material for Manufacturing Portland cement. The studied area known as Suren Mountain and Avroman Mountain located in Halabja governorate in Kurdistan region, northeast Iraq. These mountains elongated from NW to NE Khurmal town. This area is placed at (46° 00´ 36" and 46° 05" 50") East and (35° 17´ 02" and 35° 20´ 50") North. The studied area is divided in to four traverses (Ahmad Awa „A‟, Shanaw valley „Sh‟, Helanpe „H‟ and Banishar Valley „Bn‟). The present study contains field description, petrographical, mineralogical analysis, geochemical analysis and physical and mechanical properties in the main four traverse in order to evaluate the Avroman Formation. The field description shows that the lithology of this Formation is pure limestone and no any marly limestone sequence or beds, it has generally grey colour massive, hard limestone and contains joint and fracture, many macro fossils bivalve were recorded in Banishar valley such as Megalodone. From the petrographical study six microfacies were recognized in four studied sections such as Mudstone, wackstone, lithoclastic packstone, oolitic packstone to grainstone, lithoclastic bioclastic grainstone and peloidal grainstone. The fossils are relatively rare but some micro fossil were identified such as: Echinoid, Plecypod, Foram and some unknown bioclast, and petrographical study shows that the calcite is the dominant mineral phase. The mineralogical analysis using XRD shows that the calcite is a dominant mineral in the limestone samples followed by quartz as trace and little amount of dolomite. The mineralogical study of clay consists of clay minerals and non-clay minerals. The clay minerals are represented by chlorite, a prevailing mineral, and then followed by illite, montmorillonite and kaolinite. The non-clay minerals are quartz, a dominant mineral followed by calcite and very few percentage plagioclase. The insoluble residue (noncarbonate mineral) in the limestone are quartz, clay minerals and iron oxide such as hematite and pyrite. The geochemical study of limestone Avroman Formation shows that all major, minor oxides (CaO, SiO₂, Al₂O₃, Fe₂O₃, MgO, SO₃, P₂O5, TiO₂ and MnO) are within the standard specification for manufacturing Portland cement. The high calcium carbonate content of the limestone which is about 97 % must be mixed with the available clays in the VIII

study area for producing Portland cement with high limestone saturation factor and adjusted silica and alumina ratio. The limestone saturation factor 90 and 95 were used to estimate the mixing ratio of both limestone and clay materials in different proportions and estimating the clinker composition. The estimated clinker composition and calculated mineral phase (alite, belite aluminate and ferrite) that in agreement with standard specification for production of Portland cement. The comparing results of silica and alumina ratios as well as hydraulic modules, minimum burning temperature, burnability index and liquid phase for studied samples with standard specification of Portland cement show that most of the studied samples are in agreement with these standards. The physical properties (apparent porosity, bulk density, apparent specific gravity, water absorption and natural moisture content) show that most of the studied samples are adjusted with natural ranges for carbonate rocks used in cement industry. In addition the low moisture content of studied samples indicates that the dry process can be used in manufacturing cement. From the results of compressive strength of study samples ranges indicated that most of samples are classified moderate strong to very strong. Classification of Siliciclastic sediment shows that the soil samples of the studied area are sandy mudstone except sample C3 is muddy sandstone.

IX

List of Contents

Subject

Page

Acknowledgments

………………………………………………………………... VII

Abstract

………………………………………………………………... VIII

List of Contents

………………………………………………………………... X

List of Figures

………………………………………………………………... XIII

List of Tables

………………………………………………………………... XVI

List of Appendices ………………………………………………………………... XVIII

Chapter one Introduction 1.1 1.2 1.3 1.4 1.5 1.5.1 1.5.2 1.5.3 1.6

Preface ……………………………………………………………………... Location of Studied area …………………………………………………... Geological Setting ………………………………………………………… Previous study ……………………………………………………………... Methodology ………………………………………………………………. Field Work …………………………………………………………………. Laboratory Work …………………………………………………………... Office Work ………………………………………………………………... The Aim of the study ……………………………………………………….

1 3 5 8 10 10 16 17 17

Chapter Two Petrology, Petrography and Mineralogy 2.1 2.2 2.2.1 2.2.2 2.2.3 2.3.4 2.3 2.3.1 2.3.2 2.3.2.1 2.3.2.2 2.3.3 2.4 2.4.1 2.4.2

Preface ……………………………………………………………………. Petrology …………………………………………………………………. Ahmad Awa Section ……………………………………………………... Shanaw Valley Section …………………………………………………... Helanpe Section ………………………………………………………….. Banishar Valley Section ………………………………………………….. Petrography ………………………………………………………………. Rating System ……………………………………………………………. Constituent in Carbonate rocks …………………………………………… Allochemical Components (Grains) ……………………………………… Orthochemical (Cement) ………………………………………………… Petrography of the studied Samples ……………………………………… Mineralogical Analysis …………………………………………………... Mineralogical Components of Limestone ………………………………... Mineralogical Components of Soil ………………………………………. X

18 18 18 19 19 22 25 25 27 27 28 29 38 38 42

2.4.2.1 Non-oriented Soil Samples (Bulk sample) ……………………………….. 42 2.4.2.2 Oriented Soil Samples ……………………………………………………. 43 2.5 Insoluble Residue (I.R) …………………………………………………... 51

Chapter Three Geochemistry of Raw Materials 3.1 3.2 3.2.1 3.2.11 3.2.1.2 3.2.1.3 3.2.1.4 3.2.1.5 3.2.1.6 3.2.1.7 3.2.1.8 3.2.1.9 3.2.1.10 3.2.2 3.3 3.3.1 3.3.2 3.3.2.1 3.3.2.2 3.3.2.2.1 3.3.2.2.2 3.3.2.2.3 3.3.2.3 3.3.2.3.1 3.3.2.3.2 3.3.2.3.3 3.3.2.3.4 3.3.2.4 3.3.2.4.1 3.3.2.4.2 3.3.2.4.3 3.3.2.4.4

Preface ………………………………………………………………… Geochemistry of the studied samples as cement raw materials ………... Geochemistry of Limestone ……………………………………………. Calcium Oxide (CaO) and Loss on Ignition (LOI) …………………….. Silica (SiO2) ……………………………………………………………. Alumina (Al₂O₃) ………………………………………………………. Ferric Oxide (Fe₂O₃) …………………………………………………… Magnesium Oxide (MgO) ……………………………………………... Alkalis (Na₂O and K₂O) ……………………………………………….. Sulfur (SO₃) and Phosphorous (P₂O5) …………………………………. Other Minor Constituent Such as Titanium Oxide (TiO₂) &Manganese Oxide (MnO) ………………………………………………………….. Insoluble Residue ………………………………………………………. Chemical Moduli of Raw Materials (Limestone) ……………………… Geochemistry of Soil …………………………………………………… Mixing and Clinker Production ………………………………………… Raw mix design ………………………………………………………… Clinker Production ……………………………………………………... Theoretical chemical Composition of Clinker …………………………. Calculation of Clinker Parameter (Ratio) ……………………………… Limestone Saturation Factor (LSF) …………………………………….. Silica Ratio (SR) ……………………………………………………….. Alumina Ratio (AR) or Alumina Modulus (AM) ……………………… Clinker Phase …………………………………………………………... Alite C₃S ……………………………………………………………….. Belite C₂S ………………………………………………………………. Aluminate C₃A ………………………………………………………… Ferrite C4AF ……………………………………………………………. Clinker Properties ………………………………………………………. Hydraulic Modulus (HM) ……………………………………………… Minimum burning Temperature (MBT) ………………………………... Burnability Index (BI) ………………………………………………….. Liquid Phase at the burning Zone ………………………………………

54 54 54 55 56 56 57 60 61 64 64 65 65 70 71 71 73 73 74 74 75 76 77 77 78 78 78 81 81 81 81 82

Chapter Four „Physical & Mechanical Properties of Raw Materials‟ 4.1 4.2

Preface ……………………………………………………………………... Physical Properties ………………………………………………………… XI

83 83

4.2.1 4.2.2 4.2.3 4.2.4 4.2.5 4.3 4.4

Apparent Porosity ………………………………………………………….. Bulk Density ……………………………………………………………….. Apparent Specific Gravity …………………………………………………. Water Absorption ………………………………………………………….. Natural Moisture Content ………………………………………………….. Mechanical Properties (Uniaxial Compressive Strength UCS) of Limestone. Texture Analysis of the studied Soil ……………………………………….

83 86 87 87 88 90 93

Chapter Five „Summary, Conclusions and Recommendations‟ 5.1 5.2

Summary and Conclusions ………………………………………………… 95 Recommendations …………………………………………………………. 97

References……………………………………………………………… 98 Appendices

XII

List of Figures Figure No.

Title

Page No.

Fig.1.1

Satellite image representing the location of the studied area.

4

Fig.1.2

Geological map of the North eastern Iraq (after Lawa et al., 2013 with 7 indication of the studied area.

Fig.2.1

Bitumen on the surface of limestone in Ahmad Awa section.

18

Fig.2.2

Tiger print on the surface of limestone in Ahmad Awa section

19

Fig.2.3

Calcite vein in limestone of Avroman Formation in Shanaw valley 20 section

Fig.2.4

Brecciated limestone in Shanaw valley section

20

Fig.2.5

Fracture in Avroman Formation in Shanaw valley section

21

Fig.2.6

Massive bed of Avroman Formation in Shanaw valley section

21

Fig.2.7

Large slumped or slided down rocks from Avroman Formation in 22 Helanpe section

Fig.2.8

Vuggy porosity in Banishar valley section

23

Fig.2.9

Thin discontinuous horizon of Iron oxide also occurred within the 23 limestone in Banishar valley section.

Fig.2.10 Large fossil Megalodone Bivalve in Banishar valley section pale brown 24 colour. Fig.2.11 Large fossil Megalodone bivalve filled by calcite and milky colour 24 appears in Banishar valley section. Fig.2.12 Dunham s Carbonate Rock Textural Classification (1962) with 26 modifications by Embry& Klovan (1971) (From Loucks, et al., 2004). Fig.2.13 A13; Microphotograph (40X) showing intraclastic peloidal grainstone 31 X:without taining Y: with stained red colour indicated calcite is more dominants.Sh8;Microphotograph showing highly fractured mudstone with stained Y without stained X. H12; photograph showing bioclastic mudstone with same Foram F Fig.2.14 A1.Bioclastic

grainstone with

lithoclasts

and contain fragment 32

Pelecypode P. and Echinoid E. A3.Bioclastic grainstone with lithoclasts. A4.Bioclastic grainstone with lithoclasts contain large Echinoid (e).A6 Bioclastic packstone-grainstone with intraclasts and with some coated

XIII

grain.40X. Fig.2.15 A7: Bioclastic grainstone, lithoclasts with superficial ooid (s) the oblate

33

ooid are formed around bioclasts. A10: Bioclastic grainstone with. A11: Peloidal grainstone with intraclasts and some Foram F. A15: Bioclastic grainstone with some Foram F (Textularia).40X. Fig.2.16 Sh1: Fin grain limestone (mudstone) with highly fractured filled by 34 calcite Sh3: this slide consist two parts lift side recrystallized limestone and right side highly fractured mudstone. Sh3ppl2: very highly deformed mudstone with fractured filled by calcite. Sh7: highly deformed wackstone.40X. Fig.2.17 Sh10: (mudstone) highly fractured filled by calcite.Sh12: fine micrital 35 Peloidal Packstone with contain Foram (F). H2 and H9: intraclastic wackstone with Contain vein of calcite.40X Fig.2.18 H10: Oolitic packstone to grainstone, which consist ghost of ooids. H12. 36 Bioclastic Mudstone with some Foram (F). Bn1ppl: Intraclastic wackstone to packstone with leaved grain (L). Filled by secondary calcite. The stylolite (s) appearance in slide Bn1ppl2. 40X. Fig.2.19 Bn3: Mudstone with highly fractured filled by calcite. Bn4: Intraclastic 37 Wackstone with some grain the originally fossil which replacement by calcite Bn7: Extraclastic packstone filled with micrite. Bn9: Intraclastic packstone may Contain same ooids.40X. Fig.2.20 X-ray diffraction for limestone Ahmad Awa section (A5)

40

Fig.2.21 X-ray diffraction for limestone Shanaw valley section (Sh7)

40

Fig.2.22 X-ray diffraction for limestone Helanpe section (H10)

41

Fig.2.23 X-ray diffraction for limestone Banishar valley section (Bn10)

41

Fig.2.24 X-ray diffraction pattern of oriented clay fraction of Ahmad Awa area 45 in different treatment stage. Fig.2.25 X-ray diffraction for clay sample from Ahmad Awa area (Bulk sample).

45

Fig.2.26 X-ray diffraction pattern of oriented clay fraction of Shanaw valley near 46 Igneous body in different treatment stages. Fig.2.27 X-ray diffraction for clay sample from Shanaw valley near igneous body Fig2.28

46

X-ray diffraction pattern of oriented clay fraction of Banishar valley in 47 different treatment stages.

XIV

33

Fig.2.29 X-ray diffraction for soil sample form Banishar valley (Bulk sample).

47

Fig.2.30 X-ray diffraction pattern of oriented clay fraction of Helanpe area in 48 different treatment stages Fig.2.31 X-ray diffraction for soil sample form Helanpe area (Non-oriented).

48

Fig.2.32 X-ray diffraction pattern of oriented clay fraction of Helanpe area 49 in different treatment stages. Fig.2.33 X-ray diffraction for soil sample from Helanpe area (Bulk sample).

49

Fig.2.34 X-ray diffraction pattern of oriented clay fraction of Khurmal area 50 in different treatment stages Fig.2.35 X-ray diffraction for soil sample from Khurmal area (Bulk sample).

50

Fig.2.36 X-ray diffraction for (I.R) limestone Ahmad Awa section (A13).

52

Fig.2.37 X-ray diffraction for limestone (I.R) Shanaw section (Sh1).

52

Fig.2.38 X-ray diffraction for limestone (I.R) Helanpe section (H4).

53

Fig.2.39 X-ray diffraction for limestone (I.R) Banishar section (Bn9).

53

Fig.3.1

Variation of average percentage of (A-SiO₂, B-Al₂O₃, C-Fe₂O₃, D- 59 MgO,

E-CaO, F-Na₂O, G-K₂O, and H-IR) of different sections with

normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda, 1985). Fig.3.2

Linear relation between CaO% and other oxides of the studied samples.

63

Fig.3.3

Schematic illustrations of the typical proportions of phases for the 80 formation of Portland clinker minerals as a function of the progressive kiln temperature. The figure is adapted from the (Hewlett, 1998) in (Aldieb and Ibrahim, 2010).

Fig.4.1

Linear relationship between Apparent porosity and (A- Bulk density, 89 and B- water absorption) of the studied samples.

Fig.4.2

Classification of Siliciclastic sediments based on sand, silt and clay 94 content after Folk (1974) in Tucker (1991), for studied samples of Soil.

XV

List of Tables

Table No.

Title

Page No

Table 1-1

Location and Field description of Ahmad Awa section limestone.

11

Table 1-2

Location and Field description of Shanaw valley section limestone.

12

Table 1-3

Location and Field description of Helanpe section limestone.

13

Table 1-4

Location and Field description of Banishar valley section limestone

14

Table 1-5

Location and Field description samples of soil.

15

Table 2-1

Semi quantitative analysis for studied carbonate rock samples.

39

Table 2-2

Semi quantitative analysis of non-clay mineral in the Soil samples.

42

Table 2-3

Semi quantitative analysis of clay minerals in the soil sample (all

44

value Table 3-1

in percentage).

WSU (Washington state University) XRF precision, Limit of

57

determination (2-sigma) for geochemistry of limestone. Table 3-2

Results of chemical analyses of the Avroman Formation with LSF, SR

58

and AR values. Table 3-3

Sodium equivalent values for the studied samples using the equation

62

derived from (Shafer, 1987). Table 3-4

Comparison between the average compositions of the studied

67

Limestone from Ahamad Awa section with Normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda 1985). Table 3-5

Comparison between the average composition of the studied limestone

67

from Shanaw valley section with that normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda 1985). Table 3-6

Comparison between the average composition of the studied limestone

68

from Helanpe section with that normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda 1985). Table 3-7

Comparison between the average composition of the studied

68

limestone from Banishar valley section with that normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda 1985). Table 3-8

Comparison of the results of chemical analysis for the studied samples with Iraqi standard specification NO.5 (1984) for the production ordinary Portland cement. XVI

69

Table 3-9

Chemical composition of Soil of Avroman area and it is comparison

71

with the normal clay according to (Pentti, 1932 in: Shah, et al., 2007) elsewhere in the world (all values are percentage). Table 3-10 Summary of practical steps to calculate the composition of the mixture

73

and clinker expected with some properties. Table 3-11 Mineralogical composition percent Portland cements, (after Newman,

80

2003 and Brandt, 2009). Table 4-1

Physical properties of limestone Avroman Formation of the studied

85

area. Table 4-2

Physical and mechanical properties of some limestone rocks

86

(Chatterjee, 2004). Table 4-3

Steps for finding uniaxial compressive strength (UCS) of limestone

92

samples for each studied section. Table 4-4

Point load strength classification (After Anon, 1972).

93

Table 4-5

Grain sizes Analysis represents the percentage of Sand, Silt and Clay

94

of the samples of the Studied Area.

XVII

List of Appendices

Appendix (A): The procedure for staining a thin section of a carbonate rocks has been done according to (Dickson, 1956 in: Adam, 1987). Appendix (B): Estimate the amount insoluble residue in the raw materials by prepared 100ml HCl with 10% Concentration according to (Awad and Mashkour, 1980) procedure. Appendix (C): Weight and weight % of insoluble residue in the samples of limestone of the studied area using the concentration of N10% hydrochloric acid. Appendix (D): Chemical composition of mixture and cement clinker with produced some properties. When LSF= 90. Appendix (E): Chemical composition of mixture and cement clinker with produced some properties. When LSF = 95. Appendix (F): Iraqi standard specification (IQS). No.31 (1981) for measurement of Bulk density, Specific gravity, moisture content, apparent porosity, and Water absorption of limestone rock for production of Portland cement Appendix (G): ISRM 1985. Suggested method for determining point-load strength. Int. J. Rock Mech. Min. Sci. Geomech. Abstr. 22, pp. 53–60.

XVIII

Chapter one

Introduction

CHAPTER ONE INTRODUCTION 1.1. Preface Portland cement (often referred to as OPC, from Ordinary Portland Cement) is the most common type of cement in general use around the world because it is a basic ingredient of concrete , mortar ,stucco and most non-special grout. Cement is a fine powder produced by grinding Portland cement clinker. Portland cement clinker is a hydraulic material which consists of at least two-thirds by mass of calcium silicates (3CaO.SiO₂ and 2CaO.SiO₂), the remainder consisting of aluminium – and Ironcontaining clinker phases and other compounds (Aldieb and Ibrahim, 2010). The Portland cement is not a brand name, but a type of grade cement; it was developed in 1824 in England by Joseph Aspdin. He was granted a patent on hydraulic cement that he named it Portland cement (Krech, 1998; Bye, 1999; Hewlett, 2004). The name reflected its grey colour similarity to Portland stone. This stone is an attractive and widely used British building stone at the time, queried near Portland, England (Bye, 1999; Hewlett, 2004). He made their first batch using the same material that was used for natural cement with careful proportioning of limestone and clay. The product was heated in an oven, with much higher temperature of calcination for producing clinker, and ground it into a fine powder (Punmiaet al., 2003; Karol, 2005). Since human first started to build, they used a kind of binding material for binding stone together into solid form. Assyrians and Babylonians were among the ancient human civilizations to use clay as binder for construction purposes. Later ancient Egyptians discovered a binding agent made from lime and gypsum mortars. Further improvements were made by the Greeks and Romans who made cement that produced structures with significant strength used in early Roman architecture (Buckley, 2001). In 1780, James Parker developed Roman cement. This cement was natural and produced by calcining argillaceous limestone, nodules found in certain clay deposits. This development patented in 1796 (Ghosh, 2002). In England before developing Portland cement, natural cement was discovered (Bates, 1960).

1

Chapter one

Introduction

The cement production in Iraq was initiated in 1949 where the first plant was established with production capacity of about 8.000 ton per year as a result of economic and constructional progress and project development (Al-Dabbas et al., 2013).There was an increase in demand of this material and to serve new companies and plants to cover local market needs. The general southern company for cement is one of the three companies that were distributed in North, Central and South of Iraq. This includes eight factories in: Al-Najaf, Al-Kufa, Karbala, Al-Sadaa, Al-Muthana, Al-Samawa, and UmQasire. Their conventional products are two kinds of cement, normal and resistance. The first cement plant constructed in Sulaimani, Kurdistan region was Sarchinar cement plant in 1954. The plant started production in 1957 using the wet process for producing Portland cement. The capacity was 350 tons of clinkers per day producing normal Portland cement, salt resistant cement and low heat cement (Ministry of industry and minerals, 1975), this plant continues till 2009. It was closed due to the occupation of the surround areas by urbanization. A second cement plant located 20Km Southwest Sulaimani City at Tasluja areas started production since 1986 with annual production capacity of 2,300,000 tons (Izdihar-USAID, 2007). In Kurdistan region NE-Iraq every year a huge amount of Portland cement is produced and used for construction of building, roads, and high ways and other local purposes. The cement industry in the region has been established and expanded very rapidly in last seven years. Today, two cement companies produce Portland cement (Bazian and Mass cement companies) beside the Tasluja cement company. Industrialization of Portland cement depended on the raw materials such as limestone, clay, and gypsum which were considered as the key to the success of cement industry. Nowadays, in Sulaimani city Sinjar Formation (Tertiary rock) is the main raw material for producing cement, but this study tries to find new suitable resources as alternative raw material for Sinjar formation which is the „Avroman Formation,‟ (Upper Triassic rock) to be used for cement industry in the future. In this case an assessment must be done for raw materials especially limestone and clay of the studied area because successful clinker production demands a defined mixture of limestone, clay and corrective additives.

2

Chapter one

Introduction

1.2. Location of the Studied Area The studied area is represented by Suren and Avroman Mountains (are locally called Shakhy Hawraman) which are located within Halabja Governorate in north-eastern Iraq. The studied area is located between the latitudes (35 ° 17ʹ 02ʺ and 35 ° 20ʹ 50ʺ) to the north and longitudes (46 ° 00ʹ 36ʺ and 46 ° 05ʹ 56ʺ) to the east. Suren Mountain is bordered by the Sharazoor plain at the southwest. This mountain is elongated from northwest to northeast of Khurmal town. This mountain is represented by the Avroman Formation which is located in Qulqula Khwakurk sub zone (Buday and Jassim, 1987) and Zagros Suture Zone (Baziany, 2014). The outcrops of the Avroman Formation were indicated in NE Iraq on the border with Iran. Four sections (traverse) are selected in the studied area for detail study which are Ahmad Awa „A‟, Shanaw valley „Sh‟, Helanpe „H‟, and Banishar valley „Bn‟ (Fig. 1.1). The location of these studied areas as is below: 1-Ahmad Awa village section A: it is located at latitudes (35° 17ʹ54ʺ, 35° 17ʹ 02ʺ) and longitudes (46° 03ʹ16ʺ, 46° 04ʹ 36ʺ) which is 3.7 Km to the East of Khurmal town (Fig.1.1). 2-Shanaw Valley section Sh: it is located at latitudes (35° 18ʹ46ʺ, 35° 19ʹ 38ʺ) and longitude (46° 04ʹ36ʺ) 2.3 Km to the North -West of Ahmad Awa village (Fig.1.1). 3-Helanpe Village section H: it is located at latitudes (35° 18ʹ46ʺ, 35° 19ʹ 38ʺ) and longitudes (46° 03ʹ16ʺ, 46° 04ʹ 36ʺ) 4.6 Km to the North east of Khurmal town (Fig.1.1). 4-Banishar Valley section Bn: it is located at latitudes (35° 19ʹ38ʺ, 35° 20ʹ 30ʺ) and longitudes (46° 00ʹ36ʺ, 46° 01ʹ 56ʺ) 3.9 Km to the North-West of Khurmal town (Fig.1.1). The 8 clay samples were collected from four sections and around the studied area (Fig.1.1).

3

Chapter one

Introduction

Figure 1.1: Satellite Image representing the location of the studied area.

4

Chapter one

Introduction

1.3. Geological Setting The Avroman limestone comprises of about 800m of light grey, brownish, sometimes milky white, thick-bedded to massive, hard limestone(Jassim and Golf, 2006).The carbonate of the Avroman formation is very pure with minimum clastic contain and very rarely dolomitised. The biostratigraphy of the Avroman limestone Formation which outcropped in the Zalam valley, Banishar and Kani Seif areas was evaluated. The oldest beds of the Triassic of the Avroman area are light grey, hard, massive, locally dolomitised limestone similar to the Dachstein facies of the Alpine-Carpathian mountain ranges (Jassim and Golf, 2006). The range of macrofossils and microfossils is extremely large the most typical Avroman limestone fauna comprises megalodones (this appear in Banishar Valley section) accompanied by encrusted Forams and Algae, Gastropods and Brachiopods (Jassim and Golf, 2006). The age of Avroman limestone Formation which did not get the status of a Formation, has not been proved by any fossil up to 1975. Fossil found were made in 1976 in the Avroman range. These are according to Cicha and Salaj (in Buday et.al, 1977 in Buday, 1980) Megedodires indicating the Noric age of the typical light colored, massive part dolomitized limestone. The stratigraphy of the Formation is obscured by intensive deformation inside Iraqi and metamorphism in the Iranian territories; the deformation caused the imbrications and possible thrusting and sliding of the rock (Karim, 2007), and thus it is difficult to identify the lower, middle and upper parts of the Formation. The Avroman Formation is overlain by Qulqula Radiolaria Formation and Merga Red Beds in Iraq and Iran respectively (Fig.1.2). Underlying Formation is not exposed and it is said that the environment of the deposition is shallow which is represented by an isolated platform with agitating water. The Avroman Limestone which is known as the Bisitoun Shoal Limestone in Iran was deposited on the Bisitoun Micro-continent (Bordenave & Hegre, 2005). It represents a big and narrow continental slab which extends over 400 km from SW Iran (Lurestan) to the Iraqi Kurdistan region (Ibrahim, 2009). The area covered by high mountains that have the same zagros trending of northwest –southeast. There are many wide and narrow valleys, between the mountains such as Suren mountain (2328m high), and Hawraman mountain (2540m high) (Baziany, 2014).The studied area is situated within the western Zagros Fold- Thrust

5

Chapter one

Introduction

Belt, which developed from the basin fill of the Neo-Tethys and the collision of the Iranian and Arabian plate. Structurally, the studied area is located within imbricated and thrust zone (Buday and Jassim, 1987). More recently, Lawa, et al., 2013 redefined the thrust and imbricate zone into a single unit referred to as the zagros imbricated zone. According to Dunningtone (1958) the thrust zone has developed during the Alpine orogeny that started from the upper cretaceous time and continued through the tertiary where it emphasized during the Pliocene time. According to (Buday and Jassim 1987) in the tectonic subdivision of Iraq the Avroman Formation is put in the Qulqula-Khwakurk Subzone and located in Zagros suture zone according to (Baziany, 2014). Avroman subzone and Qulqula subzone are part of Qulqula-Khwakurk zone (Jassim and Goff, 2006). This zone comprises deep water passive margin sediment (radiolarian chert and limestone) and volcanic of the southern Neo-Tethys which opened in late Tithonian- Cenomanian time it includes a huge allochthonous block of carbonate interpreted as the sheared off cover of a micro continent (Jassim and Goff.2006). The area is characterized by obscured anticlines and synclines which have been stacked together as very thick and tight packages which were overturned toward southwest or even over thrusted (Baziany, 2006). Most of these structures suffered from thrusting. Stocklin (1974), called the studied area “ Crushed Zone” because it is highly deformed on large and small scale, even one can see micro fracture, micro fault and micro fold under polarized microscope.

6

Chapter one

Introduction

Figure. 1.2: Geological map of the North eastern Iraq (after Lawa et al, 2013) with indication of the study area.

7

Chapter one

Introduction

1.4. Previous Studies Bolton (1958) in Buday (1980) introduced the Avroman Formation for the first time. He described the formation as a sequence of light cooler thick bedded partly crystalline limestone with interbedded of marly limestone with thickness about 600m. The age of this formation is upper Triassic. Jassim and Golf (2006) studied the tectonostratigraphy of the Qulqula-Khwakurk zone. They mentioned that the Avroman limestone outcrops in the Avroman subzone of the Qulqula-Khwakurk zone which was abducted and sutured to the Arabian plate during the late Cretaceous. They also added that the subzone extend into adjacent area is much wider .this subzone is thrust over the Qulqula subzone and also showed that this Formation is unconformable overlain by clastic of the Red Beds series. Baziany (2006) studied the stratigraphy and sedimentology of Qulqula conglomerate Formation. He showed that in the Avroman-Halabja areas the conglomerate is nothing except calcareous and lithified Quaternary (recent or Pleistocene) sediments; the conglomerate beds have dip angles nearly the same as the slop of the south western side of the Avroman and Suren mountain. The conglomerate at these localities consists of limestone breccia which has the origin of proximal alluvial fan, slide debris and possibly fault breccia. Karim (2007) studied the stratigraphy and lithology of the Avroman formation. He stated that the formation is composed of pure limestone without marl and dolomite and also mentioned that the main constituents of the formation are Oncolite, Oolith, Pellet and fossil, and the environment of the deposition was shallow agitating water. Karim and Baziany (2007) studied the Qulqula conglomerate formation at Avroman-Halabja area. They found that there is no occurrence of Qulqula conglomerate formation in Halabja-Avroman area and this Formation is studied in detail in the same area which is overlaying Qulqula Radiolarian Formation. They showed that the lithology of this Formation at this area consists of thick beds of badly sorted angular pebbles, boulders and blocks of lithified limestone. These two authors concluded that most of the clasts are derived from Avroman Formation.

8

Chapter one

Introduction

Ali (2007) studied the geology and hydrology of the Sharazoor-Peramagroon Basin. He mentioned that Halabja-Khurmal sub basin contains many large springs such as (Zalm, Chawg and Biara springs) all the surface run off and ground water discharge of this sub basin are drained to the Darbanikhan reservoir by Zalim and Byara streams. He also showed that all rocks of the basin are sedimentary and range in age from Triassic to recent. The stratigraphic units are grouped as karstic and this area is a part of the region influenced by the Mediterranean climatologically system. Ibrahim (2009) studied the tectonic style and evolution of the NW segment of the Zagros Fold –thrust Belt, he showed that ZFTB has been segmented in to the NW segment (Iraqi zagros) and the SW segment (Iranian zagros). He showed that the tectonic nature and evolution of this segment (especially thrust zone) has still remained problematic. Baziany (2014) studied the depositional system and sedimentary basin analysis of the Qulqula Radiolarian Formation of the zagros suture zone. He recognized two basins for the deposition of Qulqula Radiolarite based on the occurrence of igneous bodies, red clay stone, sedimentary mélange and Avroman limestone. These basins are Radiolarite basin, which is located in Sharbazher area, and Hawraman basin, which is located in Hawraman area. Ali Talabani (2014) studied the stratigraphy and sedimentology of Avroman Formation. He mentioned that can be recognized three units within the studied succession; each unit has a specific characteristic feature (U1, U2, & U3). These units are separated by marker beds of recrystallized dolomitic limestone and brecciated limestone.

Many authors studied the carbonate rock as a raw material for cement industry such as Yazdeen (1990), Thanoon and Yazdeen (1990), Thanoon (1999), Al-Ali (2004), Khalid (2006), Al-Ali, et al., (2008), Thanoon and Khalid (2010), Hussein (2010), Hussein(2012), Salih, et al.,(2012), Mirza (2012), Al- Auweidy (2013) and Al-Dabbas, et al.,(2013). Previously no one studied the Avroman limestone Formation for cement industry; this study is the first evaluation of carbonate rock of Avroman Formation.

9

Chapter one

Introduction

1.5. Methodology The methods that are used in this study include the following stages:

1.5.1. Field work The field work of this study began with selecting the four suitable sections (Ahmad Awa village „A‟, Shanaw valley „Sh‟. Helanpe village „H‟ and Banishar valley „Bn‟). The limestone and soil samples were collected along these four traverses; each collected samples weighted about 2kg. The thickness of limestone beds cannot be measured in all the sections due to thrusting and intensive deformation of Avroman Formation. The instrument used for collecting samples was map, GPS, hammer, hand lens and camera. The first section located East Ahmad Awa village; 16 samples were collected representing (A1 to A16) from the Avroman limestone Formation in this area. The description of each samples is shown in (Table 1-1), and 2 soil samples were also collected in this area which are (C1 and C2) shown in (Table 1-5). The second selected section located in Shanaw valley; 13 samples were collected representing (Sh to Sh13) from the Avroman limestone Formation along the direction of the valley, and one sample of soil was collected (C3) near this study area. The description each samples shown in (Table 1-2 and 1-5). The third study section was in the Helanpe village towards the Shanaw valley. In this section 11 samples were collected representing (H1 to H11). The samples are taken randomly in many large block of Avroman limestone Formation which was slumped or slided and three samples of Soil were collected in this area which includes (C5, C6, and C7), the description of each sample is shown in (Table 1-3 and 1-5) The last section was in Banishar valley in this section 10 sample was collected toward the direction of valley from Avroman limestone Formation representing samples (Bn1 to Bn10). As well as one samples of Soil was collected in this area include (C4). The description of each sample as in (Table 1-4 and 1-5). As well as sample C8 taken in the Khurmal area.

10

Chapter one

Introduction

Table (1-1) Location and Field description of Ahmad Awa section Limestone Sample number

Location of samples by Field description GPS and elevation

A1

A2

A3

A4

A5

A6

A7

A8

A9

A10

A11

A12

A13

A14

Elev: 874 N 35° 17' 14.5" E 46° o4' 28.1" Elev:875 N 35° 17' 16.2" E 46° 04' 28.5" Elev:875 N 35° 17' 17" E 46° 04' 28.7" Elev:887 N 35° 18' 08.7" E 46° 04' 29.7" Elev:890m N 35° 17' 19" E 46° 04' 29" Elev:888m N 35° 17' 22" E 46° 04' 28.9" Elev:890m N 35° 17' 22.3" E 46° 04' 29.1" Elev:800m N 35° 17' 24.7" E 46° 04' 23.5" Elev:800m N 35° 17' 25.6" E 46° 04' 22.7" Elev:785m N 35° 17' 26.1" E 46° 04' 23.1" Elev:747m N 35° 17' 32.5" E 46° 04' 25" Elev: 768m N 35° 17' 34.1" E 46° 04' 21.6" Elev:760m N 35° 17' 35.7" E 46° 04' 21.6" Elev:760m N 35° 17' 35.7" E 46° 04' 21.6"

11

Massive

pale

grey

fine

crystalline limestone and contain joint and fracture and also contain veins of calcite, tiger print appear on the surface of the beds.

Chapter one A15

A16

Introduction Elev:752m N 35° 17' 44.2" E 46° 04' 15.8" Elev:733m N 35° 17' 48.7" E 46° 04' 12.2"

Massive light grey crystalline limestone contains brown colour bitumen.

Table (1-2) Location and Field description of Shanaw valley section Limestone Sample number

Location of samples by Field description GPS and elevation

Sh1

Sh2

Sh3

Sh4

Sh5

Sh6

Sh7

Sh8

SH9

Sh10

Sh11

Elev:727m N 35° 18' 42.8" E 46° 04' 36.3" Elev:740m N 35° 18' 44" E 46° 04' 36.7" Elev:735m N 35° 18' 45.8" E 46° 04' 36.1" Elev:737m N 35° 18' 47.2" E 46° 04' 35.8" Elev:745m N 35° 18' 49.6" E 46° 04' 33.5" Elev:761m N 35° 18' 52.4" E 46° 04' 34" Elev:786m N 35° 19' 00" E 46° 04' 34.6" Elev:806m N 35° 19' 01.4" E 46° 04' 34.1" Elev:808m N 35° 19' 03.6" E 46° 04' 34" Elev:612m N 35° 19' 05.5" E 46° 04' 34.8" Elev:815m N 35° 19' 09" E 46° 04' 33.7"

Massive grey colour fine crystalline some

part

limestone of

bed

contains iron oxide and tiger print appear on the surface of the bed.

Massive

milky

colour

crystalline limestone and Brecciated.

Massive grey colour fine crystalline limestone and contain Joint and fracture in some part of the bed, contains iron oxide and tiger print appears on the surface of the bed.

12

the

in

Chapter one

Sh13

Introduction Elev:860m N 35° 19' 10.7" E 46 04' 36.6" Elev:870m N 35° 19' 10.7" E 46° 04' 36.0"

Table (1-3) Location and Field description of Helanpe section Limestone Sample number

Location of samples by Field description GPS and elevation

H1

H2

H3

H4

H5

H6

H7

H8

H9

H10

H11

Elev:1070m N 35° 20' 23.2" E 46° 03' 32.6" Elev:1078m N 35° 20' 21.3" E 46° 03' 37.4" Elev:1133m N 35° 20' 06.9" E 46° 03' 46.5" Elev:1200m N 35° 20' 05" E 46° 03' 53.7" Elev:1240m N 35° 20' 14.6" E 46° 04' 00.7" Elev:1268m N 35° 20' 02.2" E 46° 04' 01.4" Elev:1284m N 35° 19' 54.8" E 46° 04' 20" Elev:1255m N 35° 19' 54.7" E 46° 04' 06.7" Elev:1159m N 35° 20' 06.1" E 46° 04' 43.8" Elev:1150m N 35 20' 09.6" E 46 04' 53" Elev:1148m N 35° 20' 11.2" E 46° 04' 58"

13

Thick pale to dark grey colour

crystalline

limestone.

Thick pale grey to milky colour limestone

fine

crystalline with

vugy

porosity and contain veins of calcite.

Chapter one

Introduction

Table (1-4)Location and Field description of Banishar valley section Limestone Sample number

Location of sample by Field description GPS and elevation

Bn1

Bn2

Bn3

Bn4

Bn5

Bn6

Bn7

Bn8

Bn9

Bn10

Elev:694m N 35° 20' 14.1" E 46° 01' 40.4" Elev:710m N 35° 20' 15.1" E 46° 01' 41.8" Elev:715m N 35° 20' 17.2" E 46° 01' 43.5" Elev:731m N 35° 20' 19" E 46° 01' 45" Elev:744m N 35° 20' 21" E 46° 01' 45.5" Elev:738m N 35° 20' 30.5" E 46° 01' 47" Elev:770m N 35° 20' 39.8" E 46° 01' 35.3" Elev:766m N 35° 20' 40.5" E 46° 01' 32.3" Elev:798m N 35° 20' 41.2" E 46° 01' 28.4" Elev:750m N 35° 20' 40.4" E 46° 01' 25.8"

14

Massive pale greyish to pale

brown

colour,

crystalline limestone with Iron

oxide

and

vuggy

porosity.

Alteration milky to pinkish colour crystalline limestone with Iron oxide contains Brecciated porosity.

and

vuggy

Chapter one

Introduction

Table (1-5) Location and Field description samples of Soil Sample number

Location

Location of sample Field description by GPS and elevation

C1

Behind Ahmad Awa

C2

Behind Ahmad Awa

C3

Near the Shanaw valley section

C4

In Banisher valley section

C5

In Helanpe

C6

In Helanpe

C7

In Helanpe

C8

In Khurmal area

Elev:893m N 35° 17’ 11.4’’ E 46° 04’ 30.4’’ Elev:166m N 35° 17’ 55.6’’ E 46° 05’ 12.4’’ Elev:1000m N 35° 18’ 52.8’’ E 46° 05’ 13.2’’ Elev:770m N 35° 20’ 39.8’’ E 46° o1 135.3’’ Elev:1098m N 35° 20’ 15.9’’ E 46° 03’ 42.9’’ Elev:1118m N 35° 20’ 08.5’’ E 46° 03’ 45.1’’ Elev:1184m N 35° 20’ 04.7’’ E 46° 03’ 49.2’’ Elev:550m N 35° 18’07.3’’ E 46° 00’ 51.1’’

15

Recent valley deposited.

Chapter one

Introduction

1.5.2. Laboratory Work Laboratory

work

includes

petrographical

study,

mineralogical

analysis,

geochemical analysis, physical and mechanical analysis. For petrographical study, 26 thin sections were prepared in University of Sulaimani Department of Geology and the transmitted microscope model (Magai) was used. To distinguish between the calcite and dolomite content, the alizarin was prepared according to the method (Dickson, 1965 in: Adam, 1987); this procedure is outlined in appendix (A). Mineralogical analyses were conducted using X-Ray diffraction (XRD) for 4 limestone and 6 clay samples in Geosurvey in Baghdad. For clay samples, oriented and non-oriented samples were prepared following Iraqi geological survey standard work procedure, part 2 (Al-Janabi et al., 1992). The XRD pattern was obtained with a Shimadzu XRD 7000 instrument operating at 45 KV and 40 mA using Cu-Kα radiation. Diffraction pattern was between 3°-50° (2Ɵ) for limestone samples while the diffraction pattern for clay samples was between 3°-50° (2Ɵ) for non-oriented samples (Bulk sample) and between 3°-20° (2Ɵ) for oriented spacemen. Crystalline phase was identified and evaluated by XRD. The insoluble residue content in 4 samples of limestone and 2 clay samples have also been analysed by using XRD model panalytical 5°-70° (2Ɵ)in Department of Physics Basra University, and the name of each mineral was found by using a chart in (Tucker, 1988). Geochemical analysis was obtained by XRF type (Thermo-ARL Advant´XP+ Xray fluorescence spectrometer) for 46 limestone samples at GeoAnalytical Laboratory, School of Earth and Environmental Science, Washington State University while for 8 clay samples were obtained by test (ASTM C114-03) in Mass Cement Factory in Sulaimani city. Insoluble residue was obtained by test method (Awad and Mashkour., 1980), and the procedure was described in appendix (B), in University of Sulaimani Geology Department. The Physical properties of carbonate rock were established including (Apparent porosity, apparent specific gravity, Bulk density, Water absorption and Moisture content) in Department of Geology University of Sulaimani, using (IQS No.31 (1981)) procedure described in appendix (F).

16

Chapter one

Introduction

The mechanical properties of the limestone samples are done in Engineering Laboratory in Geology Department at University of Sulaimani to determine the strength of limestone by point load test and converted to unconfined compressive strength. The samples were Irregular and core samples and they are classified according to the Anon (1972) classification. Grain size analysis for clay samples was made in Ministry of Construction and Housing, Sulaimani Construction Laboratory using sieving and hydrometer according to the procedure (ASTM D 422-63).

1.5.3. Office Work The information collected from petrography, mineralogy, geochemical, physical and mechanical analysis was used for writing this thesis with reference to many published works.

1.6. The Aim of the Study The aims of the present study are:1- Assessment of the carbonate rock from Avroman limestone Formation for manufacturing of Portland cement. 2- Evaluation of soil deposit in the same area for cement industry.

3- Finding an alternative for the carbonate rocks of Sinjar Formation to be used in cement Industry. Due to development of building and using huge amount of Portland cement in Kurdistan every year; this study is conducted to find for the alternative carbonate rocks of Sinjar Formation which are the main raw materials for producing Portland cement in Sulaimani city.

17

Chapter two

Petrology, petrography and mineralogy

CHAPTER TWO PETROLOGY, PETROGRAPHY AND MINERALOGY 2.1. Preface In this chapter, the focus is on Petrology, petrography and mineralogy of raw materials in all studied sections of Avroman area.

2.2. Petrology 2.2.1. Ahmad Awa section (A): The Avroman Formation in this section is composed of variation of colour pale grey to dark grey, massive bedded of limestone, very hard, crystalline limestone, fine grain. It contains little joint and fracture and many veins in the limestone which are filled by Calcite are visible. In the upper part of this section bituminous appears in the block of limestone (Fig.2.1). Tiger print structure appears on the limestone beds (Fig.2.2).

Figure (2.1): Bitumen on the surface of limestone in Ahmad Awa section.

18

Chapter two

Petrology, petrography and mineralogy

Figure (2.2): Tiger print on the surface of limestone in Ahamad Awa section.

2.2.2. Shanaw valley section (Sh): The Avroman Formation at this section is characterized by pale grey to dark grey colour, but in some positions milky colour, massive bedded, very hard, coarse crystalline calcite. This section is characterized by calcite vein in the limestone but they are more than the veins in section (A) (Fig.2.3) and also by fine to coarse grain limestone and there are no any marly sequences or beds. In some parts of this section, brecciaed limestone appears which indicates that the tectonic affected this region (Fig.2.4). The beds contain joints and fractures(Fig.2.5). Occasionally, vuggy porosity and tiger print were observed within the limestone. The estimated thickness of limestone in this section is very huge from the mass (Fig.2.6). 2.2.3.Helanpe Village section (H) : The Avroman limestone Formation in this section represents variation in colour pale grey to dark grey and milky colour, crystalline limestone, detrital, fine to coarse grain, which has strong reaction with dilute HCl, and there are no any marly sequence or beds. The samples collected from this section represent many large block of Avroman Formation which are slumped or sliding downward (Fig.2.7) 19

Chapter two

Petrology, petrography and mineralogy

Figure (2.3): calcite vein in limestone of Avroman Formation in Shanaw valley section.

Figure (2.4): Brecciated limestone in Shanaw Valley section.

20

Chapter two

Petrology, petrography and mineralogy

Figure (2.5): Fracture in Avroman Formation in Shanaw valley section.

Figure (2.6): Massive bed of Avroman Formation in Shanaw valley section.

21

Chapter two

Petrology, petrography and mineralogy

Figure (2.7): Largeblocks slumped or slided down from Avroman Formation in Helanpe section.

2.2.4. Banishar Valley section (Bn): The Avroman Formation in this section is characterized by pale greyish to pale brown,(lower part) and pinkish to white and milky colour (upper part), respectively and also massive, detrital, very fine crystalline and highly jointed, well fractured beds of limestone. Moreover it has strong reactions with dilute HCl, and there are no any marly sequences or beds. The limestone in this section is softer than the other studied sections, because some excavation features and vugy porosity were observed within these beds which are formed by dissolution of calcite (Fig.2.8). In addition, some thin discontinuous horizon of Iron oxide also occurred within the limestone in this section (Fig.2.9). Large fossil bivalve: Megalodone recognized within the limestone as well (Figs.2.10 and 2.11).

22

Chapter two

Petrology, petrography and mineralogy

Figure (2.8): Vuggy porosity in Banishar valley section.

Figure (2.9): Thin discontinuous horizon of Iron oxide also occurred within the limestone in Banishar valley section.

23

Chapter two

Petrology, petrography and mineralogy

Figure (2.10): Large fossil Megalodone Bivalve in Banishar valley section pale brown colour.

Figure (2.11): large Megalodone bivalve filled by calcite and milky colour appear in Banishar Valley section.

24

Chapter two

Petrology, petrography and mineralogy

2.3-Petrography In order to confirm field data, (26) thin sections were prepared for petrography (Microfacies Analysis) from the four sections which are selected for the purpose of examination under the polarized microscope. Petrographical study is required for discriminating between calcite and dolomite using staining thin section by polychlorinated Alizarin red (Alizarin red solution) and potassium ferriccyanide (pot ferricyanid) according to the method (Dickson, 1965 in: Adam, et al., 1984).This procedure is outline in appendix (A). These thin sections were examined to prepare staining by Alizarin red and studied under a microscope. It shows that the mineral calcite polarizer is purple red colour, but it will not affect the dolomite and does not change its colour(Fig.2.13). The study also paid attention to the components of structural rocks limestone as diagnosis of some pelloid, ooid, oncoid and common of planktonic foraminifera as well as the measurement of sizes granule mineral calcite and dolomite. Sometimes quartz is also seen by using standard microscopy because of its direct effect and significant role in determining the degree of homogeneity of the mixture of raw and effectiveness when burning.

2.3.1 Rating system Several researchers give more than a classification of calcareous rocks based on the implications of the various descriptive terms of rocky ingredient and the origin of these rocks and depositional environment. Each petrographer aims to reach a certain goal depending on the type of the study and the foundation purpose. Among the most important classifications used in this field is Dunham, 1962, which limestone can be classified on the basis of depositional texture in to (mudstone to grainstone). The Dunham‟s classification represented in (Fig.2.12) is widely used particularly in the field description of carbonate rocks; the former group is further subdivided as to whether or not the grains and mud-supported. If the rock consists of less than 10% grain, it is called Mudstone; if it is mud supported with greater than 10% grain, it is called a Wackstone. If the rock is grain supported, and if the grains have shapes that allow for small

25

Chapter two

Petrology, petrography and mineralogy

amounts of mud to occur in the interstices it is called packstone. If the rock is grain supported, but there is no mud between the grains, it is called grainstone. The Dunham classification was modified by Embry and Klovan (1971). Boundstone is splitted in to Bafflestone, Bindstone and Framestone which describe type of organisms that build up the framework (Fig.2.12). The term Rudstone (clast-supported limestone conglomerate) and Floustone (matrix supported limestone conglomerate) were added to be used for carbonate intraformational conglomerate. They are made of material deposited in an adjacent part of the same environment and then redeposited, but in this study they did not appear when the thin sections examined under microscope.

Figure (2.12): Dunham s Carbonate Rock Textural Classification (1962) with modifications by Embry& Klovan (1971) (From Loucks, et al., 2004). 26

Chapter two

Petrology, petrography and mineralogy

2.3.2Constituent in carbonate rocks The studied thin sections from four sections of studied area show two most important component of carbonate rocks which are: Allochemical components and Orthochemical components.

2.3.2.1 Allochemical components (Grains) A-Skeletal Grains/Bioclasts Many different types of skeletal grains and their bioclast are distinguished within the current study such as Foraminifera, pelecypode, Echinoid, (Figs.2.14A1, A4, 2.15A11, A15, 2.17Sh12, 2.18H12) are very common types of skeletal grain which are observed within the thin sections of limestone of Avroman Formation but, their percentage is very few to rare because some of them are highly affected by diagensis process. Some of other fragmentation which represents the shell fragments and cannot exactly be classified.

B-Non-skeletal Grains The non-skeletal grains are represented by intraclasts, extraclast, ooid, pellets (peloid), oncoid and non-carbonate constituent grains such as Iron minerals; these are observed in the studied samples. Intraclast - A fragment of penecontemporaneous, commonly weakly consolidated, carbonate sediment that has been eroded and redeposited, generally nearby, within the same depositional sequence in which it formed (Folk, 1959 and 1962). Extraclast - A detrital grain of lithified carbonate sediment (lithoclast) which is derived from outside the depositional area of current sedimentation (Folk, 1959). Ooid (Oolith) - a spherical to ellipsoidal grain, 0.25 to 2.00 mm in diameter, with a nucleus covered by one or more precipitated concentric coatings (cortical layers) with radial and/or concentric orientation of constituent crystals (Scholle, 2003). Nuclei typically consist of detrital terrigenous grains, skeletal fragments, or pellets and peloids, and coatings can have a variety of compositions. A rock composed dominantly of ooids is

27

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Petrology, petrography and mineralogy

termed an “oolite”. That term is commonly misused, however, to describe the constituent ooid grains (Scholle.2003). Oncoid - A coated grain of algal (but not red algal) or microbial origin that is coarser than 2 mm in diameter; a spheroidal form of microbial stromatolite showing a series of concentric (often irregular or scalloped) laminations. These unattached stromatolites are produced by mechanical turning or rolling, exposing new surfaces to microbial/algal growth (Scholle, 2003). Peloid -It is a comprehensive descriptive term for polygenetic grains composed of micro and cryptocrystalline carbonate. Peloids are commonly devoid of internal structures but may contain fine grained skeletal debris and other grains. The term was proposed in order to replace the widely used term (pellet) which, for many authors had become a synonym for 'fecal pellet' (McKee ad Gutschick 1969) in (Slaih, 2013). Peloids are common in shallow-marine tidal and subtidal shelf carbonates and in reef and mud mounds, but are also abundant in deep-water carbonates. By contrast to the abundance of peloids in tropical shallow-marine carbonate, peloids are rare or absent in non-tropical cool water carbonates (Flugl, 2010). In the studied carbonate rocks the two types of peloids (fine and course) were common.

2.3.2.2. Orthochemical (cement) Cement consists of coarse crystalline material (>10 microns), which occupies the majority of the original pore space, cavities and fissures within the rocks. Different types of spary calcite are cement formed by neomorphisum, recrystallization and cementation (Qader, 2006). A-Micrite or Microcrystalline Calcite: it is carbonating sediment in the form of grains less than 5µmdiameter. Much of it is formed in the basin of deposition, either as precipitate from sea water or from the disintegration of the hard parts of organisms such as green algae. The term carbonate mud is also used for this fine sediment, although strictly mud includes material of clay –and silt size (up to 62µm) (Adams, et al., 1984).

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Petrology, Petrography and Mineralogy

B-Sparry calcite, sparite or spar refers to crystals of 5µm or more in diameter. Much of it is coarse, with crystals commonly up to 1 mm in size. It is usually pore-filling cement and thus may form in a rock a long time after deposition of the original allochems and micrite (Adams, et al., 1984).

2.3.3. Petrography of the studied samples The Ahmad Awa section: The studied thin sections in Ahmad Awa show that the limestone succession contains shallow environment, detrital limestone which mostly consists of bioclastic (grainstone, ooid packstone to grainstone and peloidal grainstone) (Figs.2.14A1,A6 and 2.15A11). The Bioclast consists of fragment skeletal grain of Echinoid, plecypod and some Foram (Figs.2.14A4, A6 and 2.15A11, A15). The ooids are mostly superficial (i.e.: few laminas arranged around relatively large nucleus of bioclasts and lithoclast (Fig.2.15A7). Nearly, all the clasts and skletones suffer from more or less calcification

process,

and

the

cement

materials

are

mostly

sparry

calcite,

packstone/grainstone deposits that mostly within tidal channels. Microscopic study shows that the samples mostly consist of grainstone Microfacies. The Shanaw valley section shows that the limestone succession contains shallow environment which mostly consists of fine grain limestone (mudstone).This Microfacies is also found at different levels in the measured section. These mudstones sometimes highly deformed and fractured, are filled with calcite. Mudstones devoid of any skeletal grain recorded in (Figs.2.16Sh1, Sh3, and 2.17 Sh10) and also the recrystallization limestone appears in this section that the original texture may be mudstone (Fig.2.16 Sh3). The other Microfacies are highly deformed wackstone and Bioclastic pelloidal packstone (Figs.2.16Sh7, 2.17Sh12). The skeletal grain is Foram (Fig.2.17Sh12). Nearly all the clasts and skeletons suffer more or less from micritization process. The Helanpe section: the limestone succession in this section mostly consists of these Microfacies: intraclastic wackstone, bioclastic mudstone and oolitic packstone to grainstone (Figs.2.17H2, H9) and (Figs.2.18H10, H12). The bioclastic mudstone found in this section is composed predominantly of Foram, Figure (2.18H12).The upper part of this section shows lithoclastic wackstone with highly joint and fracture which are filled by

29

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calcite and highly deformed (Fig. 2.18 H12).The ghost ooid is observed in the upper part as well and it is shown in (Fig.2.18H10). The Banishar valley section: In this section the microscopic studies revealed the existence of these microfacies (intraclastic wackstone to packstone, mudstone, intraclastic wackstone and extraclastic packstone), (Fig.2.18Bn1) and (Figs.2.19Bn3, Bn4, Bn7). The mudstone is found at different location in measured section; these mudstones are highly fractured and filled with calcite without any skeletal grain (Fig.2.19Bn3, Bn9). The orthochem in this section is mostly micrite, so it can be Saied that micrital limestone is indicative of low energy depositional environment. Iron oxide has been seen in this section which indicated insoluble residue; stylolite also appears in this section (Fig.2.18Bn1 ppl2). The limestone in this section mostly indicated the tidal flat and laggonal limestone. According to Nichols (1999) in (Essien, et al.,2012) carbonate lagoons are sites of fine grain sedimentation forming layers of carbonate mudstone and wackstone with very few grainstone and packstone beds deposited as wash –over near the beach barrier.. Microfacies packstones to grainstones including Foraminifera and intraclasts that were deposited in an environment of relatively agitated water like that in shoals and microfacies wackstones to mudstone deposited in restricted shallow quiet water zone like a lagoon (Hashemi Azizi, et al., 2013). The grain size of calcite for all studied samples generally range about (50- 120) Micron, according to (Chatterjee, 20004) the acceptable size of calcite in carbonate rock for cement industry is 125 micron, this means all studied sample can be easily use in this industry.

30

Chapter two

Petrology, petrography and mineralogy X

Y

Figure (2.13): A13; Micro photograph (40X) shows intraclastic peloidal grainstone X: without staining Y: with stained red colour indicated calcite is more dominant. Sh8; photograph shows highly fractured mudstone with stained Y without stained X. H12; micro photograph shown bioclastic mudstone with same Foram F.

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Chapter two

Petrology, Petrography and Mineralogy

Figure (2.14) A1 Bioclastic grainstone with lithoclasts and contain fragments of Pelecypode P. and Echinoid E. A3.Bioclastic grainstone with lithoclasts.A4.Bioclastic grainstone with lithoclasts contain large Echinoid (e).A6: Bioclastic packstone- grainstone with intraclasts and with some coated grain. 40X. 32

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.15) A7: Bioclastic grainstone, lithoclasts with superficial ooids (s) the oblate ooids are formed around bioclasts.A10: Bioclastic grainstone with intraclasts.A11: peliodal grainstone with intraclasts and some ForamF.A15: Bioclastic peliodal grainstone with some Foram F (Textularia).40X. 33

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.16) Sh1: fine grained limestone (mudstone) with highly fractured filled by calcite. Sh3: This slide consists of two parts left side recrystallized limestone and right side highly fractured mudstone.Sh3ppl2: highly deformed mudstone with fractures filled by calcite cement.Sh7: highly deformed wackstone.40X. 34

Chapter two

Petrology, Petrography and Mineralogy

Figure(2.17) Sh10: Mudstone highly fractured filled by calcite cement.Sh12: fine micrital peloidal packstone with contain Foram (F). H2 and H9: Intraclastic wackstone with contain vein of calcite.40X 35

Chapter two

Petrology, Petrography and Mineralogy

Figure(2.18)H10: Oolitic packstone to grainstone, which consists of ghost of ooids.H12: Bioclastic Mudstone with some Foram (F).Bn1ppl: Intraclastic, wackstone to packstone with leaved grain (L) filled by secondary calcite. The stylolite(s) irregular type with low amplitude appearance in slide Bn1ppl2. (40X).

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Chapter two

Petrology, Petrography and Mineralogy

Figure (2.19) Bn3: mudstone with high fracture filled by calcit.Bn4: Intraclastic wackstone with some grains originally fossil replaced by calciteBn7: Extraclastic packstone filled with micrite.Bn9: Intraclastic packstone may contain same ooids. 40X.

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Chapter two

Petrology, Petrography and Mineralogy

2.4. Mineralogical Analysis: The mineralogical information of carbonate rocks used in cement industry can be very useful in predicting the severity of wear out that will occur in the crushing and grinding machinery in addition to the kiln refractory lining and burning behaviour of the material in the kiln (Kohlhaas, 1983 and Al-Auweidy, 2013). Although many different methods used in the definition of minerals, X-ray diffraction is the most commonly used method to diagnose and determine their rates because it is fast and accurate analysis.

2.4.1. Mineralogical components of limestone X-ray diffraction pattern of limestone samples showed that in all the samples from sections (A5, Sh7, H10 and Bn10), the dominant mineral phase is calcite (CaCO₃), whereas the calcite appears to be predominant and highly participates in the samples which is more than 99% of the total constituent (Table 2-1). Peaks of calcite are quiet clear in the X-ray diffraction pattern of all the samples (Figs, 2.20, 2.21, 2.22 and 2.23),in the rang (2Ɵ) 3°50°,its identified by the major reflection at (3.03A°, 2Ɵ=29.43°), as well as another less intense reflection at(3.87A°, 2Ɵ= 23.04°),(2.49A°, 2Ɵ= 36°),(2.29A°, 2Ɵ= 39.43°), (2.08A°, 2Ɵ= 43.53°),(1.91A°, 2Ɵ= 47.53°) and (1.88A°, 2Ɵ= 48.55°). Most CaO required for cement raw materials comes from calcite. The quartz phase is scarce appearing as trace especially in samples (A5), d space =3.35A°, 2Ɵ=26.6°. In all the studied samples, the dolomite is obscured except sample Bn10 (Fig. 2.23) which is present as less dominant phase after calcite and the percentage is about 29.9% (Table, 2.1). The major peak reflection of dolomite at (2.888A°, 2Ɵ=31°), as well as another less intense reflection at (2.01A°, 2Ɵ=45°) and (2.12A°, 2Ɵ =41.2°) (Fig, 2.23).

38

Chapter two

Petrology, Petrography and Mineralogy

Table (2.1): Semiquantatitive analysis for studied carbonate rock samples.

Sample No.

Calcite %

Dolomite %

Quartz %

Total

A5

99.80

0.00

0.20

100.00

Sh7

99.80

0.00

0.00

100.00

H10

99.80

0.00

0.00

100.00

Bn10

70.10

29.90

0.00

100.00

39

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.20). X-ray diffraction for limestone Ahmad Awa section (A5).

Figure (2.21). X-ray diffraction for limestone Shanaw section (Sh7).

40

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.22). X-ray diffraction for limestone Helanpe section (H10).

Figure (2.23). X-ray diffraction for limestone Banishar section (Bn10).

41

Chapter two

Petrology, Petrography and Mineralogy

2.4.2 Mineralogical components of soil 2.4.2.1 Non-oriented soil samples (Bulk Sample) The X-ray diffraction pattern (Figs, 2.25, 2.27, 2.29, 2.31, 2.33, 2.35, 2.37, 2.39) of the representative clays from studied area reveals the presence of non-clay minerals identified are (calcite, quartz and plagioclase). The percentage of non-clay minerals associated with clay samples were calculated using peak area calculation (Table, 2-2), which reveals that quartz is the dominant non-clay mineral in all the samples. The major peak reflection at (3.35A°, 2Ɵ =26.6°) as well as another less intense reflection at(2.46A°, 2Ɵ=36.56°),(4.26A°, 2Ɵ=20.85°), (2.28A°, 2Ɵ=39.49°) and (2.13A°, 2Ɵ=42.48°). All the studied clay samples show that the quartz is the major non-clay mineral associated with clay except sample number C3 and C6 in which the calcite is the dominant. Calcite is designated in all the samples their strong basal reflection appears at 3.03A° that corresponding with 2Ɵ (29.43°). Plagioclase is another non-clay mineral which is identified in sample C3, it is % is about 17.6% and the major basal reflection at (3.19A° , 2Ɵ=28°). The present plagioclase may be derived from teregeneaus rock surrounding the studied area especially the basic volcanic rock (Basalt) that associated with Qulqula Formation. Table (2.2) Semi quantative analysis of non-clay mineral in the soil sample. Sample No.

Calcite%

Quartz%

Plagioclase%

Total %

C1

25.0

75

0.0

100

C3

69.6

12.8

17.6

100

C4

1.6

98.4

0.0

100

C5

44.5

55.3

0.0

99.8

C6

64.0

34.0

0.0

98.0

C8

5.9

93.6

0.0

99.6

42

Chapter two

Petrology, Petrography and Mineralogy

2.4.2.2. Oriented Soil samples For oriented clay mineral, three analytical procedures were conducted. These are (i) (Normal sample) (ii) diffraction of glycolated samples that were solvated with ethylene glycol in an oven at 60C for 2 hours. (iii) Diffraction of samples that were heated at 550 C for two hours in the furnace oven. XRD analyses at measuring ranging between 2° - 20° (2Ɵ) diffraction result were obtained after these treatments. When the air-dried samples (Normal samples) were diffracted, peaks developed on the diffractogram (Figs., 2.24, 2.26, 2.28, 2.30, 2.32, 2.34 and 2.35). These diffractogram after treatments (glycolated and heating 550C°) revealed that three main clay minerals appear namely chlorite, illite and montmorillonite which appeared in all the samples, except in samples (C6 and C8) in which montmorillonite disappeared. Moreover, kaolinite appears as trace clay mineral in sample C4 its % is about 4.12% and the major basal reflection at (7.01A°, 2Ɵ=12.63°). The chlorite appears to be predominant and participates in the total constituents with a rate higher than the other clay minerals. The percentage and type of clay minerals are illustrated in (Table 2-3). From diffraction results (Figs.,2.24, 2.26, 2.28, 2.30, 2.32, 2.34 and 2.35) chlorite is identified by the major peak reflection at (7.01A°, 2Ɵ=12.63°) as well as lesser reflection at (14.2A°, 2Ɵ=6.23°). Chlorite is unaffected by glycolation and generally survives after heat treatment (550 C°), which can be seen in all the samples. It is associated relatively with high MgO which is present in the clay samples (Al-Ali, et al,2008). Illite is identified by major reflection at (9.86A°, 2Ɵ=8.96°), and it is not affected by the two prescribed treatment (glycolated and heat treatment 550C°). Montmorillonite is identified in samples (C1, C3, C4, C5) by major peak reflection at (12.9A°, 2Ɵ=6.85°) in (C4 and C5)and lesser reflection at (4.85A°, 2Ɵ=18.3°) in (C1, C3). When the montmorillonite is glycolated and dried the diffraction pattern showed that peaks of the samples were widened and shifted, but by heating the samples at 550C°, the peaks collapsed.

43

Chapter two

Petrology, Petrography and Mineralogy

Table (2.3): Semi quantitative analysis of clay minerals in the soil sample (All value in percentage).

Sample No.

Chlorite

Illite

Montmorillonite

Kaolinite

Total

C1

77.30

15.20

7.60

0.00

100.10

C3

67.40

12.30

20.30

0.00

100.00

C4

52.26

33.12

10.50

4.12

100.00

C5

93.30

0.95

5.70

0.00

99.95

C6

98.00

2.0

0.00

0.00

100.0

C8

94.40

5.60

0.00

0.00

100.00

44

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.24) X-ray diffraction pattern of oriented clay fraction of Ahmad Awa area in different treatment stages

Figure (2.25). X-ray diffraction for soil sample from Ahmad Awa area (Bulk sample). 45

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.26). X-ray diffraction pattern of oriented clay fraction of Shanaw valley near igneous body in different treatment stages.

Figure (2.27). X- ray diffraction for soil sample from Shanaw valley near igneous body (Bulk sample).

46

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.28) X-ray diffraction pattern of oriented clay fraction of Banishar valley in different treatment stages.

Figure (2.29). X-ray diffraction for soil sample form Banishar valley (Bulk sample).

47

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.30) X-ray diffraction pattern of oriented clay fraction of Helanpe area in different treatment stages.

Figure (2.31). X-ray diffraction for soil sample form Helanpe area (Bulk sample).

48

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.32) X-ray diffraction pattern of oriented clay fraction of Helanpe area in different treatment stages.

Figure (2.33). X-ray diffraction for soil sample from Helanpe area (Bulk sample).

49

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.34) X-ray diffraction pattern of oriented clay fraction of Khurmal area in different treatment stages.

Figure (2.35). X-ray diffraction for soil sample from Khurmal area (Bulk sample).

50

Chapter two

Petrology, Petrography and Mineralogy

2.5. Insoluble residues Analysis (I.R) This technique (Awad, S.A and Mashkour, M. 1980) is used to distinguish those minerals that cannot be dissolved in hydrochloric acid (non- carbonate minerals), such minerals are clay minerals, quartz and some of the heavy minerals (hematite and pyrite). Based on this technique, 50 samples of limestone have been tested; the detailed of the procedure is depicted in appendix (B). Moreover, the percentage and weight of insoluble residue for each sample have been determined which are between (0.20-2.86) %, (0.032- 0.590) gm respectively for limestone samples, see appendix (C). According to the results, the limestone is considered as a pure limestone. The XRD technique was used to identify insoluble residue minerals. For each section, only one sample is taken which are (A13, Sh1, H4, and Bn9). According to the result, the sample of limestone contains quartz, clay mineral, hematite and pyrite, but hematite and pyrite can be shown as trace minerals (Figs .2.36, 2.37, 2.38, 2.39). In sample Sh1, it can be said that the quartz mineral does not exist or it is very rare, if it is compared with other samples (Fig.2.41).So the relationship between quartz, clay mineral and IR is directly proportional.

51

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Petrology, Petrography and Mineralogy

Figure (2.36). X-ray diffraction for (I.R) limestone Ahmad Awa section (A13).

Figure (2.37). X-ray diffraction for limestone (I.R) Shanaw section (Sh1).

52

Chapter two

Petrology, Petrography and Mineralogy

Figure (2.38). X-ray diffraction for limestone (I.R) Helanpe section (H4).

Figure (2.39). X-ray diffraction for limestone (I.R) Banishar section (Bn9) 53

Chapter three

Geochemistry of Raw Materials

CHAPTER THREE GEOCHEMISTRY OF RAW MATERIALS 3.1. Preface Limestone and other carbonate rocks are extremely valuable raw materials and are widely used in industry, although the construction and cement manufacturing industries are generally the main consumers. Strategic evaluation of national or regional limestone resource or site specific reserve estimations need to involve more than a basic geological appraisal and should include laboratory determinations of physical, mechanical, chemical and mineralogical properties of the stone. The evaluation also needs to include a comparison with national or international specifications for each potential end use. This chapter describe the preferred laboratory test results for evaluating the limestone of Avroman Formation and clay deposits from recent valley deposits in the same studied area for production of ordinary Portland cement.

3.2. Geochemistry the studied samples as cement raw materials Table 3-2 displays the results of chemical analysis of cement raw materials which are compared with results of Duda (1985), who determined the acceptable limits of raw materials for cement industry as well as the results compared to normal limestone (Clark, 1924 and Amin, et al., 2008). Portland cement consists mainly of lime (CaO), silica (SiO₂), alumina (Al₂O₃), and ferric oxide (Fe₂O₃) compounds which constitute the bulk of the raw mix. The combined content of these four oxides (major constituents) is approximately 90% of the cement weight and the remaining (minor constituents) 10% consists of magnesia (MgO), alkalis (Na₂O and K₂O) , chloride (Cl) , SO₃ , TiO₂ , P₂O5 and MnO (Al-Dabbas, et al,2013).

3.2.1. Geochemistry of limestone The chemical composition of limestone reflects its mineralogical composition. The major elemental chemistry of limestone of these four sections (Ahmad Awa, Shanaw valley, Helanpe and Banishar valley sections) are given in (Table 3-2). It is evident from this table that the limestone samples display these constituents:

54

Chapter three

Geochemistry of Raw Materials

3.2.1.1. Calcium Oxide (CaO) and Loss On Ignition (LOI) Calcium oxide (CaO) is the highest constituent of limestone; the concentration of CaO in all studied sections is very high. It is more than 53.09% except sample Bn10 which is equal 46.13% (Table 3-2). The average reached (55.17, 55.62, 55.12 and 54.47 %) in (A, Sh, H and Bn) respectively (Tables 3-4, 3-5, 3-6, and 3-7). These percentages agree with normal limestone (Clark. 1924 and Amin, et al., 2008) and (Duda, 1985). On heating (Calcination) limestone form lime (CaO) which is a basic oxide and used in cement manufacture to react with other oxides (Al₂O₃, SiO₂, and Fe₂O₃). proper lime content is limited due to the lower early strength produced when lime content is too low, and unsoundness when it is high (Duda, 1985 and Neville, 2010). High lime content is associated with early strength. In order to increase the strength, it is necessary to raise the lime content, or grind finer or both (Al.Auweidy, 2013). But higher temperature is required to burn the high lime mixtures (Neville, 2010). The limestone loses about 45% of its weight during calcination. The LOI for studied samples in (A, Sh, H and Bn) sections ranges between (42.55 -43.73%), (42.6443.65%), (42.32-43.89%) and (42.71-44.52%) respectively (Tables 3-2, 3-4, 3-5, 3-6, 3-7). These percentages are in agreement with (Duda, 1985) because they are more than 38% in all the studied sections. The high content of LOI in the studied samples is mostly contributed by carbonate minerals. The CaO content in the limestone shows positive correlation with CaCO₃ content (Fig3.2A). The major component of limestone has an LOI value of 44% and IR of 0.0% (Hawkins, et al., 2003). The CaO shows negative correlation with the silica (Fig.3.2B). The negative correlation between CaO and SiO₂ is due to the fact that CaO (from calcite) and SiO₂ (from quartz) are from two different mineral phases and they are not related. The CaO show negative correlation with Iron, magnesium, Alumina, Titania, and manganese (Fig. 3.2 C, D, E, F, and G), and these negative correlations are due to high purity of limestone.

55

Chapter three

Geochemistry of Raw Materials

Kofel (1984) classifies the carbonate rocks into 7 groups depending on CaO and LOI or CaCO₃ % content as:Carbonate rocks

Percentage CaCO₃

Limestone, high purity

>95

Marl Limestone

95-85

Lime marl

85-70

Marl

70-30

Clay marl

30-15

Marl clay

15-5

Clay

<5

Accordingly, the studied samples from the selected area (Table 3-2) are classified as high purity limestone which CaCO₃ for all the samples >97% except samples (H1, H3 and Bn10) which are (94.75, 95.82 and 82 % CaCO₃) and classified as marl limestone and lime marl respectively.

3.2.1.2. Silica (SiO₂) Silica (SiO₂) appear as impurity in limestone in the range (0.00 to 1.68 %) in all the four sections(Table 3-1) and the average reached (0.44%) in A, (0.12%) in Sh, (0.04%) in H and (0.2%) in Bn) in (Tables 3-4, 3-5, 3-6, 3-7) respectively. This is an acceptable limit for cement industry if compared with normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda, 1985). The limestone of Avroman Formation has variable amount of (SiO₂) which is contributed by quartz as insoluble residue (Figs.2.36….2.39). Variation of SiO₂ is shown in (Fig.3.1A)

3.2.1.3. Alumina (Al₂O₃) Alumina is the second largest impurity in the limestone and both the Al₂O₃ and SiO₂ concentration in the limestone usually originate from the clay mineral of the surrounding area. The Al₂O₃ content of studied samples is generally less than 0.86% (Table 3-2) and the average reached (0.17%) in A, (0.06%) in Sh, (0.25%) in H and (0.163 %) in Bn) sections (Tables 3-4, 3-5, 3-6 and 3-7) respectively. This range is an acceptable

56

Chapter three

Geochemistry of Raw Materials

limit for manufacturing of Portland cement if compared with normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda, 1985). Variation of Al₂O₃ is shown in (Fig.3.1B).

3.2.1.4. Ferric oxide (Fe₂O₃) The iron in the form of oxides and sulphides occurs as impurity in the limestone, which if present in higher amount, can cause deterioration in the building construction (Amin, et al., 2008), (Shah, et al., 2007) and (Amin, et al., 2012). In the limestone, iron can be homogenously disseminated during chemical displacement of the calcium bearing iron carbonate or can be heterogeneously distributed throughout the iron- bearing strata (Amin, et al., 2008, Shah, et al., 2007, and Amin, et al., 2012).Iron compound present in limestone influence its color (Asad, 2008). According to Royak and Royak (1985) iron in the materials provides green to blue colour. There is a strong correlation between Fe₂O₃ and whiteness-degree. The whiteness-degree value increases with decreasing of Fe₂O₃ concentration if the concentration is less than 0.5%, the material is very white (Ertek and Öner, 2008). All the studied samples of limestone have low concentration of Fe₂O₃ which is less than 0.34% except sample (H1) which is equal to 1.25% (Table 3-1) and the average reached (0.06, 0.04, 0.03 and 0.08 %) in the all sections (Tables 3-4, 3-5, 3-6 and 3-7) respectively. On the other hand, an amount of Fe₂O₃ was found in the specified range of normal limestone (Clark., 1924 and Amin, et al., 2008) and (Duda, 1985), variation of Fe₂O₃ shown in (Fig.3.1C). Table (3-1) WSU (Washington State University) XRF precision, limit of Determination (2-sigma), for geochemistry of limestone Unnormalized Major Elements (Weight %) Oxide s

SiO₂ TiO₂ Al₂O₃ FeO MnO MgO CaO Na₂O K₂O P₂O5

Re plicate r2

Re plicate LOD

0.99929

0.58

0.99992

0.017

0.99949

0.16

0.99948

0.2

0.99983

0.002

0.99994

0.076

0.99976

0.064

0.99981

0.045

0.99992

0.031

0.9999

0.005

Estimate d LOI

0.966

1

SO₃ CI

0.989 0.992

0.07 0.002

57

Chapter three

Geochemistry of Raw Materials

Table (3-2) Results of chemical analyses of the Avroman Formation with LSF, SR and AR values Sample no. SiO₂ TiO₂ Al₂O₃ Fe₂O₃ MnO MgO CaO A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 Sh1 Sh2 Sh3 Sh4 Sh5 Sh6 Sh7 Sh8 Sh9 Sh10 Sh11 Sh12 Sh13 H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 Bn1 Bn2 Bn3 Bn4 Bn5 Bn6 Bn7 Bn8 Bn9 Bn10

0.22 0.17 0.03 0.49 0.47 0.02 0.93 0.55 0.24 0.02 0.51 0.22 1.46 0.0 1.68 0.07 0.07 n.a 0.25 0.02 0.63 0.06 0 0.1 0.03 n.a 0.03 0.14 0.0 1.51 0 1.05 0.06 0.04 n.a 0.51 0.11 0.0 n.a 0.01 0.11 0.17 0.45 0.16 0.31 0.05 0.37 0.15 0.1 0.13

0.011 0.004 0.004 0.013 0.011 0.001 0.005 0.021 0.009 0.014 0.01 0.01 0.008 0.011 0.009 0.013 0.005 n.a 0.07 0.003 0.002 0.003 0.004 0.016 0.016 n.a 0.005 0.009 0.0 0.108 0.002 0.125 0.02 0.002 n.a 0.033 0.017 0.002 n.a 0.002 0.038 0.011 0.018 0.015 0.05 0.007 0.016 0.004 0.003 0.003

0.15 0.08 0.04 0.24 0.21 0.01 0.07 0.36 0.16 0.26 0.21 0.14 0.17 0.25 0.15 0.21 0.05 n.a 0.14 0.04 0.04 0.04 0.02 0.06 0.13 n.a 0.04 0.16 0.0 0.86 0.01 0.8 0.09 0.01 n.a 0.32 0.11 0.03 n.a 0.02 0.17 0.23 0.34 0.21 0.22 0.08 0.24 0.04 0.04 0.06

0.02 0.01 0.02 0.13 0.07 0.0 0.02 0.1 0.09 0.1 0.05 0.06 0.07 0.07 0.05 0.05 0.01 n.a 0.04 0.01 0.07 0.03 0.01 0.01 0.09 n.a 0.01 0.15 0.0 1.25 0 0.85 0.02 0.0 n.a 0.1 0.06 0.0 n.a 0.0 0.13 0.05 0.34 0.02 0.07 0.02 0.04 0.01 0.01 0.07

0.005 0.004 0.007 0.005 0.003 0.007 0.013 0.004 0.004 0.004 0.003 0.004 0.003 0.004 0.005 0.002 0.002 n.a 0.006 0.001 0.009 0.007 0.003 0.003 0.002 n.a 0.001 0.002 0.001 0.033 0.003 0.008 0.002 0.001 n.a 0.003 0.002 0.002 n.a 0.001 0.004 0.002 0.006 0.004 0.004 0.007 0.003 0.001 0.003 0.021

0.49 0.48 0.48 0.69 0.67 0.37 0.47 0.66 0.62 0.71 0.61 0.6 0.57 0.62 0.52 0.61 0.53 n.a 0.5 0.38 0.34 0.51 0.23 0.39 0.45 n.a 0.39 0.43 0.47 0.44 0.34 0.7 0.34 0.4 n.a 0.57 0.47 0.24 n.a 0.57 0.65 0.37 0.4 0.25 0.52 0.32 0.42 0.25 0.35 8.51

SO₃ Na₂O K₂O P₂O5 Sum L.O.I Total CaCO₃ I.R.

55.3 0.048 55.86 0.0412 55.85 0.031 54.7 0.021 54.72 0.061 56.00 0.017 55.05 0.058 54.63 0.015 55.27 0.09 55.26 0.051 54.75 0.038 55.33 0.031 54.64 0.078 55.56 0.07 54.33 0.058 55.39 0.021 55.9 0.038 n.a 0.075 55.48 0.03 55.62 0.02 55.25 0.07 55.29 0.03 56.00 0.06 55.6 0.031 55.07 0.034 n.a 0.048 55.92 0.035 55.74 0.021 55.98 0.034 53.09 0.01 55.94 0.021 53.69 0.048 55.77 0.09 56.00 0.08 n.a 0.031 54.7 0.06 55.08 0.055 56.00 0.02 n.a 0.04 55.78 0.06 54.8 0.03 55.15 0.07 55.02 0.05 55.28 0.08 55.45 0.046 55.73 0.09 55.15 0.022 56.00 0.055 56.00 0.021 46.13 0.1

0.01 0.0 0.0 0.0 0.0 0.0 0.0 0.01 0.01 0.01 0.01 0.01 0.0 0.01 0.0 0.01 0.0 n.a 0.0 0.0 0.0 0.0 0.0 0.0 0.0 n.a 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.01 n.a 0.0 0.01 0.0 n.a 0.01 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.01 0.0 0.0

Not: n.a= not analysis

58

0.03 0.01 0.0 0.03 0.04 0.0 0.01 0.05 0.03 0.05 0.05 0.02 0.03 0.07 0.03 0.04 0.01 n.a 0.04 0.0 0.01 0.01 0.0 0.01 0.03 n.a 0.0 0.02 0.0 0.01 0.0 0.02 0.02 0.0 n.a 0.09 0.02 0.0 n.a 0.0 0.01 0.03 0.06 0.03 0.02 0.01 0.04 0.0 0.0 0.01

0.049 56.28 43.57 99.85 98.70 0.019 56.65 43.38 100.03 99.69 0.024 56.46 43.47 99.93 99.68 0.032 56.343 43.49 99.833 97.62 0.029 56.24 43.38 99.62 97.66 0.039 56.44 42.97 99.41 99.94 0.035 56.6 42.99 99.59 98.25 0.043 56.42 43.07 99.49 97.50 0.028 56.46 43.73 100.19 98.64 0.026 56.46 43.39 99.85 98.62 0.081 56.28 43.51 99.79 97.71 0.023 56.41 43.51 99.92 98.75 0.031 56.99 42.55 99.54 97.52 0.027 56.62 43.37 99.99 99.16 0.021 56.79 43.32 100.11 96.96 0.019 56.4 43.45 99.85 98.86 0.043 56.62 43.51 100.13 99.77 n.a n.a n.a n.a n.a 0.086 56.54 43.26 99.8 99.02 0.018 56.09 43.41 99.5 99.27 0.132 56.48 43.01 99.49 98.61 0.032 55.97 43.85 99.82 98.68 0.016 56.27 42.64 98.91 99.94 0.014 56.2 43.46 99.66 99.23 0.013 55.83 43.8 99.63 98.28 n.a n.a n.a n.a n.a 0.02 56.43 43.74 100.17 99.80 0.03 56.68 42.73 99.41 99.48 0.009 56.46 42.99 99.45 99.91 0.026 57.32 42.32 99.64 94.75 0.006 56.3 44 100.3 99.84 0.018 57.25 42.4 99.65 95.82 0.013 56.33 43.59 99.92 99.53 0.008 56.47 43.25 99.72 99.94 n.a n.a n.a n.a n.a 0.01 56.32 43.33 99.65 97.62 0.028 55.9 43.89 99.79 98.30 0.005 56.63 42.53 99.16 99.94 n.a n.a n.a n.a n.a 0.008 56.4 43.82 100.22 99.55 0.011 55.93 43.6 99.53 97.80 0.022 56.02 43.68 99.7 98.43 0.019 56.65 42.77 99.42 98.20 0.015 55.98 43.54 99.52 98.66 0.011 56.65 43.12 99.77 98.96 0.011 56.24 43.66 99.9 99.46 0.031 56.31 43.15 99.46 98.43 0.032 56.51 42.71 99.22 99.94 0.008 56.51 43.11 99.62 99.94 0.018 54.95 44.52 99.47 82.33

1.45 0.93 0.84 2.69 1.44 0.47 1.23 1.56 1.68 2.67 1.29 0.93 2.67 1.31 2.46 1.65 1.91 0.66 1.01 0.60 1.63 0.26 0.53 1.02 1.05 1.59 0.76 2.77 0.20 2.75 0.54 3.69 0.67 0.32 0.60 1.41 0.58 0.82 0.61 0.63 1.49 0.74 2.86 0.50 1.43 0.98 1.75 0.38 0.48 0.48

SR

AR

6881.03 1.29 9718.24 1.89 38765.52 0.50 3165.23 1.32 3422.53 1.68 82761.03 2.00 2051.18 10.33 2706.19 1.20 6041.73 0.96 12885.10 0.06 3223.80 1.96 6777.64 1.10 1269.57 6.08 16215.63 0.00 1112.99 8.40 11622.79 0.27 21446.67 1.17 n.a n.a 6247.76 1.39 50592.76 0.40 2988.16 5.73 23640.13 0.86 184172.13 0.00 15590.66 1.43 18561.98 0.14 n.a n.a 40586.64 0.60 8226.34 0.45 0.00 0.00 879.70 0.72 468291.67 0.00 1217.63 0.64 19385.81 0.55 45403.23 4.00 n.a n.a 2937.00 1.21 11572.55 0.65 156055.56 0.00 n.a n.a 108091.35 0.50 9268.65 0.37 7065.33 0.61 2928.53 0.66 7779.45 0.70 4742.25 1.07 22477.91 0.50 4108.52 1.32 11841.41 3.00 16819.88 2.00 10906.02 1.00

LSF

7.50 8.00 2.00 1.85 3.00 0.00 3.50 3.60 1.78 2.60 4.20 2.33 2.43 3.57 3.00 4.20 5.00 n.a 3.50 4.00 0.57 1.33 2.00 6.00 1.44 n.a 4.00 1.07 0.00 0.69 0.00 0.94 4.50 0.00 n.a 3.20 1.83 0.00 n.a 0.00 1.31 4.60 1.00 10.50 3.14 4.00 6.00 4.00 4.00 0.86

Chapter three

Geochemistry of Raw Materials 2.0 2

5.19

0.44

0.12

0.37

AV. % Al₂O₃

AV. % SiO₂

6.75 7.00 6.00 5.00 4.00 3.00 2.00 1.00 0.00

0.20

1.5

0.5

Different Sections

B- Variation of Al₂O₃ 7.90

0.66 0.54 AV. % MgO

AV. % Fe₂O₃

A- Variation of SiO₂

0.253 0.06

0.04

0.08

0.57

2.00

1.20

0.45

0.42

D- Variation of MgO

55.17 55.66 55.19 54.48 42.61

45 AV. % Na₂O

AV. % CaO

8 7 6 5 4 3 2 1 0

Different Sections

Different Sections C- Variation of Fe₂O₃

60 50 40 30 20 10 0

0.17 0.06 0.25 0.08

0 Diffrent sections

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0

0.81

1

0.300 0.250 0.200 0.150 0.100 0.050 0.000

0.280

0.005 0.000 0.003 0.001

Different Sections

Different Sections

E- Variation of CaO

F- Variation of Na₂O 0.200 2.00

0.150 AV. % IR

AV. % K₂O

0.200

0.100 0.050

0.030

0.012 0.018 0.021

0.000

1.58

1.50

1.15

1.33

1.51

1.50

Bn

B.S

1.00 0.50 0.00

Different Sections

A

G- Variation of K₂O

Sh H Different Sections

H- Variation of IR

Figure (3.1): Variation of average percentage of (A-SiO₂, B-Al₂O₃, C-Fe₂O₃, D-MgO, ECaO, F-Na₂O, G-K₂O, and H-IR) of different sections with normal limestone (Clark, 1924 and Amin, et al., 2008) , (Duda, 1985) and (BS 12: 1996)

59

Chapter three

Geochemistry of Raw Materials

3.2.1.5. Magnesium Oxide (MgO) Magnesium oxide or magnesia (MgO) in the limestone is a function of both the magnesium content of skeletal debris and also other dolomitization process due to post depositional events (Shah, et al., 2007), because increasing of MgO cause increasing the dolomitic component of limestone. Dolomite cannot be used in the manufacture of Portland cement because of its high magnesium. MgO is only present in small quantities in Portland cement ranging typically (1-5) % (Al- Auweidy, 2013). Moreover most international specification for (ordinary Portland cement) requires that the cement should not contain more than 5% MgO (less than 3% in the limestone); therefore, the identification of dolomite is crucial in the assessment of carbonate rocks for cement manufacture. Iraqi standard specification No.5 (1984) specified that the maximum percentage of MgO in limestone is equal to 5%. Too high MgO content leads to soundness (expansion) cement and consequently strength loss of the concrete, but this can be avoided by sufficiently quick quench of the clinker (Peray, 1986 and Hewlett, 2004). The quench will affect the degree of crystallization and amorphous material present known as glass (Neville, 2010) and this is form inert. It has also been claimed that still higher contents of MgO can be tolerated in cement of high iron oxide content (Bhatty, 2004). In all studied samples the concentration of MgO is low ranging between (0.37 to 0.71%) in Ahmad Awa, (0.34 to 0.53 %) in Shanaw valley, (0.24 to 0.7%) in Helanpe and (0.25 to 0.82 % except sample Bn10 which reached 8.51%) in Banishar valley section(Table 3-1) and the average is about (0.57%) in A, (0.42%) in Sh, (0.45%) in H and (1.20 %) in Bn); displayed in Tables (3-4, 3-5, 3-6, 3-7) respectively. This shows that all the samples suited with the national specification for production of (ordinary Portland cement). Moreover, this range agrees with normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda, 1985) and Iraqi standard specification No.5 (1984) (Table 3-8). MgO content of studied limestone in these sections is similar and it is below 1% because the mineralized component of each section is mostly calcite (CaCO₃) which ranges between (96.96 to 100.12 %) in Ahmad Awa section, (99.02 to 100.68 %) in Shanaw valley, (94.75 to 100.55 %) in Helanpe and (97.80 to 100.09 % except Bn10 82.33%) in Banishar valley section (Tables 3-2, 3-4. 3-5, 3-6 and 3-7). Variation of MgO is shown in (Fig.3.1D)

60

Chapter three

Geochemistry of Raw Materials

3.2.1.6. Alkalis (Na₂O and K₂O) Sodium oxide (Na₂O) and potassium oxide (K₂O) are typically addressed together because they share similar behaviour characteristics in cement manufacture and they are both found in the raw materials; they are also the most common alkalis in Portland cement (Thompson, 2012). The concentration Na₂O and K₂O are very low in all studied samples (less than 0.1%) (Table 3-1). With average percentage, Na₂O+K₂O reached (0.035, 0.012, 0.021 and 0.022%) in (A, Sh, H and Bn) sections respectively (Tables 3-4…..3-7). The variation of Na₂O and K₂O are shown in (Fig.3.1F &G). The materials have low alkali content especially sodium. High sodium concentration is more harmful to cement quality than increased potassium concentration (Strunge, et al., 1986 in Thanoon., 1999). The alkali content in raw materials that used for cement industry must be less than <1% because if it is >1%, it causes alkali to be released by cement and circulation in kiln these alkali react with the group of siliceous materials such as opal, chalcedony, tridymite produce alkali silica gel. This gel absorbs water from the cement paste and develops expansive stresses that may exceed the tensile strength of on the inner wall of kiln (Bates, 1969). This cracking or blistering can be avoid by using cement with alkali content < 0.6 %( Khalid, 2006). The low alkali content qualifies the materials for use even in low alkali cement predictor which requires the Na-equivalent to be < 0.6% according to the equation (Na-equivalent = Na₂O+ 0.658K₂O) (Shafer, 1987 and Mehta, 2001). In all the studied samples, the Na-equivalent is within this limit, see Table 3-3. The alkalis are commonly related to clay minerals of the non-carbonate fraction (Thanoon, 1999 and Shafer, 1987). According to (Table 3-2), sodium oxide (Na₂O) and potassium oxide (K₂O) are considered as trace with respect to the pure limestone chemistry.

61

Chapter three

Geochemistry of Raw Materials

Table 3-3:Sodium equivalent values for the studied samples using the equation derived from (Shafer, 1987). Sample no. A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 Sh1 Sh2 Sh3 Sh4 Sh5 Sh6 Sh7 Sh8 Sh9

Na-equivalent % 0.03 0.01 0.00 0.02 0.03 0.00 0.01 0.04 0.03 0.04 0.04 0.02 0.02 0.06 0.02 0.04 0.01 n.a 0.03 0.00 0.01 0.01 0.00 0.01 0.02

Sample no. Sh10 Sh11 Sh12 Sh13 H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 Bn1 Bn2 Bn3 Bn4 Bn5 Bn6 Bn7 Bn8 Bn9 Bn10

*n.a: not analysis

62

Na-equivalent % n.a 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.01 n.a 0.06 0.02 0.00 n.a 0.01 0.01 0.02 0.04 0.02 0.01 0.01 0.03 0.01 0.00 0.01

Chapter three

Geochemistry of Raw Materials

101

1.8

R² = 1

100

R² = 0.6164

1.6 1.4

99

1

SiO₂

Ca CO₃

1.2 98 97

0.8

96

0.6

95

0.4 0.2

94 52

53

54

A-

55

0

57

CaO

52

B-

1.4

53

54

CaO 55

0.8

R² = 0.5306

1.2

0.7

1

0.6

0.8

0.5

MgO

Fe₂O₃

56

0.6

56

57

R² = 0.2871

0.4 0.3

0.4

0.2 0.2

0.1

0 52

53

54

C-

55

CaO

56

0

57

52

1

CaO

55

56

57

R² = 0.4522

0.12

0.8 0.7

0.1

0.6

0.08

TiO₂

Al₂O₃

54

0.14

R² = 0.7039

0.9

0.5 0.4

0.06

0.3

0.04

0.2

0.02

0.1

0

0

E-

53

D-

52

53

54

CaO

55

56

57

F-

52

53

54

CaO

55

56

57

0.035

R² = 0.3485

0.03

MnO

0.025 0.02

0.015 0.01 0.005 0

G-

52

53

54

55

56

57

CaO

Figure. (3.2): linear relationship between CaO% and other oxides of the studied samples. 63

Chapter three

Geochemistry of Raw Materials

3.2.1.7. Sulfur (SO₃) and Phosphorous (P₂O₅) Sulfur (SO₃) and Phosphorous (P₂O₅) are regarded as the most undesirable impurities (RaO.2011). The presence of P₂O₅ slows down the setting time of Portland cement(Minerals Year Book, 2006). According to the Indian cement manufactures, limestone for cement making should contain less than 0.6%P₂O₅.Sulfuris volatile compounds that oxidize at different temperatures (Jackson, 1998). According to Bhatty (2004), Sulfur constitutes 0.06% by weight of the kiln feed, up to 6% by mass in some coal, and 3200 ppm in clinker. Other chemical specification may limit SO₃ and P₂O₅ to less than 1%. The SO₃ content for all the studied samples is less than 0.1% (Table 3-1) and this concides with (Duda, 1985) (Tables 3-3…..3-6), and Iraqi quality standard number .5 (1984) because the maximum percentage SO₃ reached 2.5% (Table 3-7). The average concentration of P₂O₅ in all the studied sections reached (0.03%) in A, (0.04%) in Sh, (0.014%) in H and (0.018%) in Bn, (Table 3-3, 3-4, 3-5 and 3-6).Chatterjee (2004) indicates that the allowable value of P₂O₅ content is as less than 0.06% in OPC and thus all studied samples are in agreement with this range (Table 3-1).With proper proportioning, phosphorous will improve cement properties, but in excess, hydration and strength parameters are affected (Thompson, 2012). So Jackson(1998) reports that phosphorus levels up to 0.3% in the clinker improves cement hydraulic properties and increases setting time approximately 20 minutes. According to Nurse (1952), high phosphorus concentrations cause C3S (alite) to decompose into C2S (belite) and excess lime. Moreover P₂O₅ improved the grindability of the clinkers which had a favourable effect on the porous structure, on the shape, size and colour etc. of the clinkers (Opoczky and Gavel, 2004).

3.2.1.8. Other minor constituents such as Titanium oxide (TiO₂) and Manganese oxide (MnO) The TiO₂ and MnO are present in traces in the studied limestone samples, and Rao, et al (2011) believes that the existence TiO₂ and MnO could be due to the presence of clay material in the limestone samples. The average of TiO₂ less than 0.034% and MnO is less than 0.006% in all studied samples for each sections (Tables 3-2, 3-3, 3-4, and 3-5).The TiO₂ and MnO are very low concentration and in this case they have little importance. 64

Chapter three

Geochemistry of Raw Materials

TiO₂ generally improved the grindability of the clinkers; this element has favourable effect on the porous structure, on the shape, size and colour etc. of the clinkers (Opoczky and Gavel, 2004). MnO is known as a colouring element and if concentration is less than 0.5% the material is very white (Ertek and Öner, 2008).

3.2.1.9. Insoluble residue (IR) Fifty samples analysed to determine the IR% in limestone of the studied samples and the results are shown in (Table 3-1). The average IR% in (A, Sh, H and Bn) is (1.58, 1.08, 1.15 and 1.11) % respectively. The IR is non-cementing materials which eventually exist in Portland cement. This residue affected the properties of cement, especially its compressive strength (Kiattikomol, et al., 2000 and Hani, 2011). To control the noncementing materials in Portland cement, British standard (BS 12:1996) allows the IR content to maximum limit of 1.5%. Fig.3.1H shows that the average IR in each section of studied area is nearly within this limit.

3.2.1.10. Chemical modulus of raw material (limestone) For a long time cement was manufactured on the basis of practical experience collected from the process of production. when comparing chemical analysis of Portland cement( Feed raw materials) it was found that certain relation exist between the percentage of lime on the one hand and the combination of Silica, alumina and iron oxide on the other (Alemayehu and Sahu, 2013). Table (3-2) shows the results of lime saturation factor (LSF) of limestone from Avroman Formation. The LSF is the ratio of CaO to other three main oxides (Al₂O₃, SiO₂, and Fe₂O₃). The LSF is used for kiln feed control. A higher LSF makes burning raw mix difficult (RaO, 2011). Reactivity of raw mixture for cement make is influenced greatly in pyrolysis. The pyrolysis characteristic of limestone is greatly influenced by particle size of calcite crystal, crystal shape which is a characteristic of limestone itself, and outside impurities such as Al₂O₃, SiO₂, Fe₂O₃ as well as the existence of state of accompanying minerals (Park, et al., 2004). The LSF value is very high because of high purity of limestone. According to the classification of limestone by Kofel (1984), the studied samples are considered as limestone high purity and low content (Al₂O₃, SiO₂, Fe₂O₃,

65

Chapter three

Geochemistry of Raw Materials

MgO) in all the sections and this is due to high content CaCO₃ % which is more than 97% except samples (H1, H3 and Bn10) which is (94.75, 95.8 and 82)% respectively. The LSF controls the ratio of alite to belite in clinker. A clinker with a higher LSF will have a higher proportion of alite to belite than clinker with low LSF (RaO, 2011). Typical LSF values in modern clinker are 0.92-0.98. Values above 1.0 indicate that free lime is likely to be present in the clinker. This is because, in principle a LSF= 1.0 all free lime should have combined with belite to form alite. If LSF is higher than 1.0, the surplus free lime has will not combine with anything and remain as free. Free lime (CaO) in clinker has to be closely monitored for the quality control of cement. Excess free lime results in undesirable, affected such as volume expansion, increasing setting time or reduced strength (Bonvin, et al, 1992). For the present samples the LSF ranges from (879- 468291) (Table 3-2) which highly erratic and needs to be in uniform range for cement making, therefore for calculation LSF of clinker, the LSF of raw mixture were fixed on 90 and 95.The SR (SiO2/ Al2O3 + Fe2O3) and AR (Al2O3 / Fe2O3) were compared with Iraqi standard specification number 5 (1984). The SR of the studied samples is less than 4% except a few samples of Ahmad Awa and Shanaw valley sections which reached (10.33, 6.08, 8.4 and 5.72) % in (A7, A13, A15 and Sh5) respectively because the percentage SiO₂, Al₂O₃ and Fe₂O₃ is very low in all the sections. The range AR is less than 4% in all the studied sections except a few samples, these samples include (A1, A2, Bn4 and Bn7) in which it reached (7.5, 8, 10.5 and 6) % in respectively. Some data of the studied samples (SR and AR) shown (Table 3-2) do not agree with Iraqi standard specification No.5 (1984) (Table 3-6) there for, the clay materials were used to make a mixture and repair both SR and AR to be in agreement with the standard specification.

66

Chapter three

Geochemistry of Raw Materials

Table 3-4: The comparison between the average composition of the studied limestone from Ahamad Awa section with Normal limestone (Clark, 1924 and Amin, et al., 2008) and(Duda 1985). Ahmad Awa SiO₂ TiO₂ Al₂O₃ Fe₂O₃ MnO MgO CaO SO₃ Na₂O K₂O Na₂O+K₂O P₂O5 L.O.I CaCO₃ I.R LSF SR AR

Min % 0.00 0.001 0.01 0.00 0.002 0.37 54.33 0.015 0.00 0.00 0.00 0.019 42.55 96.96 0.47 112.99 0.00 1.78

Max % 1.68 0.021 0.36 0.13 0.013 0.71 55.56 0.09 0.01 0.07 0.08 0.081 43.73 99.94 2.69 82908 10.33 7.50

AV % 0.44 0.01 0.17 0.06 0.004 0.57 55.17 0.04 0.005 0.03 0.035 0.03 43.32 98.47 1.58 13047 2.44 3.35

Normal limestone 5.19

Duda 1985 <6.75

0.81 0.54

<2.0 <0.66

7.9 42.61

<2 > 45 <1.5 <0.28 <0.2

0.38 > 38

3-5: The comparison between the average composition of the studied limestone from Shanaw valley section with that normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda 1985). Shanaw valley SiO₂ TiO₂ Al₂O₃ Fe₂O₃ MnO MgO CaO SO₃ Na₂O K₂O Na₂O+K₂O P₂O5 L.O.I CaCO₃ I.R LSF SR AR

Min % 0.00 0.00 0.00 0.00 0.001 0.23 55.07 0.02 0.00 0.00 0.00 0.009 42.64 98.28 0.20 0.00 0.00 0.00

Max % 0.63 0.07 0.16 0.15 0.009 0.53 56.00 0.075 0.00 0.04 0.04 0.132 43.85 99.94 2.77 184172 5.727 4.20

AV % 0.12 0.012 0.06 0.04 0.003 0.42 55.62 0.04 0.00 0.012 0.012 0.04 43.31 99.27 1.08 37205 1.11 2.63

67

Normal limestone 5.19

Duda 1985 <6.75

0.81 0.54

<2.0 <0.66

7.9 42.61

<2 > 45 <1.5 <0.28 <0.2

0.38 > 38

Chapter three

Geochemistry of Raw Materials

Table 3-6: The comparison between the average composition of the studied limestone from Helanpe section with that normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda 1985). Helanpe SiO₂ TiO₂ Al₂O₃ Fe₂O₃ MnO MgO CaO SO₃ Na₂O K₂O Na₂O+K₂O P₂O5 L.O.I CaCO₃ I.R LSF SR AR

Min % 0.00 0.002 0.01 0.00 0.001 0.24 53.09 0.01 0.00 0.00 0.00 0.006 42.32 94.75 0.54 879.7 0.00 0.00

Max % 1.51 0.125 0.32 1.25 0.033 0.70 56.00 0.09 0.01 0.09 0.09 0.028 44.00 99.94 3.69 468291 4.00 4.50

AV % 0.366 0.034 0.25 0.253 0.006 0.45 55.12 0.05 0.003 0.018 0.021 0.014 43.24 98.37 1.15 90530 0.92 1.24

Normal limestone 5.19

Duda 1985 <6.75

0.81 0.54

<2.0 <0.66

7.9 42.61

<2 > 45 <1.5 <0.28 <0.2

0.38 > 38

Table 3-7: The comparison between the average composition of the studied limestone from Banishar valley section with that normal limestone (Clark, 1924 and Amin, et al., 2008) and (Duda 1985). Banishar valley SiO₂ TiO₂ Al₂O₃ Fe₂O₃ MnO MgO CaO SO₃ Na₂O K₂O Na₂O+K₂O P₂O5 L.O.I CaCO₃ I.R LSF SR AR

Min % 0.05 0.003 0.04 0.01 0.001 0.25 46.13 0.021 0.00 0.00 0.00 0.008 42.71 82.33 0.48 4108 0.37 0.86

Max % 0.45 0.05 0.34 0.34 0.021 8.51 56.00 0.10 0.01 0.06 0.06 0.032 44.52 99.94 2.86 22477 3.00 10.50

AV % 0.20 0.017 0.163 0.08 0.006 1.204 54.47 0.056 0.001 0.021 0.022 0.018 43.39 97.22 1.11 9793 1.12 3.94

68

Normal limestone 5.19

Duda 1985 <6.75

0.81 0.54

<2.0 <0.66

7.9 42.61

<2 > 45 <1.5 <0.28 <0.2

0.38 > 38

Chapter three

Geochemistry of Raw Materials

Table 3-8: Comparison of the results of chemical analysis for the studied samples with Iraqi standard specification NO.5 (1984) for the production ordinary Portland cement.

sample No. MgO max.5% (Na₂O+K₂O) Max.0.6% SO₃ max.2.5% SR (1.5-4.0) AR (1.4- 3.5) A1 0.49 0.04 0.048 1.29 7.5 A2 0.48 0.01 0.0412 1.89 8 A3 0.48 0 0.031 0.5 2 A4 0.69 0.03 0.021 1.32 1.85 A5 0.67 0.04 0.061 1.68 3 A6 0.37 0 0.017 2 o A7 0.47 0.01 0.058 10.33 3.5 A8 0.66 0.06 0.015 1.2 3.6 A9 0.62 0.04 0.09 0.96 1.78 A10 0.71 0.06 0.051 0.06 2.6 A11 0.61 0.06 0.038 1.96 4.2 A12 0.6 0.03 0.031 1.1 2.33 A13 0.57 0.03 0.078 6.08 2.43 A14 0.62 0.08 0.07 0 3.57 A15 0.52 0.03 0.058 8.4 3 A16 0.61 0.05 0.021 0.27 4.2 Sh1 0.53 0.01 0.038 1.17 5 Sh2 n.a n.a 0.075 n.a n.a Sh3 0.5 0.04 0.03 1.39 3.5 Sh4 0.38 0 0.02 0.4 4 Sh5 0.34 0.01 0.07 5.73 0.57 Sh6 0.51 0.01 0.03 0.86 1.33 Sh7 0.23 0 0.06 0 2 Sh8 0.39 0.01 0.031 1.43 6 Sh9 0.45 0.03 0.034 0.14 1.44 Sh10 n.a n.a 0.048 n.a n.a Sh11 0.39 0 0.035 0.6 4 Sh12 0.43 0.02 0.021 0.45 1.07 Sh13 0.47 0 0.034 0 0 H1 0.44 0.01 0.01 0.72 0.69 H2 0.34 0 0.021 0 0 H3 0.7 0.02 0.048 0.64 0.94 H4 0.63 0.09 0.046 3.45 0.41 H5 0.34 0.02 0.09 0.55 4.5 H6 0.4 0.01 0.08 4 0 H7 n.a n.a 0.031 n.a n.a H8 0.57 0.09 0.06 1.21 3.2 H9 0.47 0.03 0.055 0.65 1.83 H10 0.24 0 0.02 0 0 H11 n.a n.a 0.04 n.a n.a H12 0.57 0.01 0.06 0.5 0 Bn1 0.65 0.01 0.03 0.37 1.31 Bn2 0.37 0.03 0.07 0.61 4.6 Bn3 0.4 0.06 0.05 0.66 1 Bn4 0.25 0.03 0.08 0.7 10.5 Bn5 0.52 0.02 0.046 1.07 3.14 Bn6 0.32 0.01 0.09 0.5 4 Bn7 0.42 0.04 0.022 1.32 6 Bn8 0.25 0.01 0.055 3 4 Bn9 0.35 0 0.021 2 4 Bn10 8.51 0.01 0.1 1 0.86

SR=Silica Ratio

AR=Alumina Ratio

n.a= Not analysis

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3.2.2 Geochemistry of Soil The major elemental of clay in the studied area is illustrated in (Table 3-9). It is clear from the table that SiO₂ varies from (42.20 to 59.35) % in Ahmad Awa area, 39.94% in Shanaw area, while in Helanpe area it ranges between (31.10 to 42.67) %, but in Banishar and Khurmal area it reaches (70.27 and 53.17) % respectively. SiO₂ is the most abundant oxide of mineral in clay. Al₂O₃ varies from (10.85 to 11.17) % in Ahmad Awa area. But reaches (12.27, 10.15, 11.46) % in Shanaw, Banishar and Khurmal respectively, while in Helanpe area it ranges between (7.88 to 13.21) %. Fe₂O₃ in Ahmad Awa area varies from (6.20 to 6.28)%but reaches (10.80, 5.96, 7.88)% in Shanaw, Banishar and khurmal respectively, while it ranges between (5.82 to 8.60)% in Helanpe area. The MgO in all the area is less than 3.45 % and Na₂O, K₂O, SO₃ are considered as trace in the clay samples. The composition of the studied clay is also compared with that normal clay (Table 3-9). SiO₂ is less than the normal clay except (C2, C4 and C8) % which are more than the normal clay, but MgO more or less is similar to that normal clay. Fe₂O₃ is quite similar to that normal clay except sample (C3). Other constituents are generally low except CaO, which is very high as compared to the normal clay (Pentti, 1932 in: Shah, et al., 2007). This is due to weathering from surrounding rocks which are mostly carbonate. In general, the compositions of the studied clay samples are in good agreement with the certified value of normal clay (Table 3-9). The clay is used as raw material for production of ordinary Portland cement because it is considered as the main source for providing SiO₂, Al₂O₃ and Fe₂O₃.

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Table 3-9: chemical composition of Soil of Avroman area and it is comparison with the normal clay according to (Pentti, 1932 in: Shah, et al., 2007) elsewhere in the world (all values are %)

Sample.No.

SiO₂

Al₂O₃

Fe₂O₃

CaO

MgO

SO₃

Na₂O

K₂O

L.O.I

ToTal

I.R

C1

42.20

11.17

6.28

14.86

2.67

0.03

0.14

0.98

21.25

99.44

68.40

C2

59.35

10.85

6.20

4.72

2.56

0.02

0.16

1.09

13.92

98.87

81.80

C3

39.94

12.27

10.80

14.09

3.45

0.03

0.17

0.93

17.54

99.22

65.60

C4

70.27

10.15

5.96

1.01

1.78

0.03

0.18

0.85

8.91

99.14

89.80

C5

42.67

13.21

8.60

10.61

2.90

0.04

0.13

0.95

20.32

99.43

81.70

C6

33.80

9.83

8.26

20.66

1.72

0.06

0.13

0.79

24.94

100.19

54.80

C7

31.10

7.88

5.82

29.30

2.27

0.07

0.30

0.74

22.30

99.78

35.20

C8 53.17 Normal clay 50.33

11.46 19.17

7.88 6.50

5.88 1.43

2.76 3.77

0.05

0.37 0.81

1.20 2.32

16.73

99.50

85.50

3.3. Mixing and clinker production 3.3.1. Raw Mix Design The purpose of calculating the chemical composition of the mixture is to find a quantitative part of the raw compounds and to obtain a chemical composition and also to get the minerals which are expected to be present in the clinker. To create an enabling mixture with specific chemical composition, identical to the specifications, the materials should be chemically suitable with the right proportion, and the proportion of the contribution of each material in the mixture should be known. (750) mixtures have been prepared for use in limited study of raw mixing. The proportion of each materials in the mixture have been calculated depending on the final equation limestone saturation factor (LSF) which was supposed by (Lea and parker, 1935) and mentioned in (Alao,1979) and modified by many, especially (Duda, 1977) . For calculating the ratio of clay and limestone in a Portland cement mixture with limited LSF: 71

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Assume the ratio of clay as X, so the limestone ratio = 1-X Any oxide % in the mixture = Oxide % in clay * X + Oxide % in Limestone * (l-X) = Oxide % in clay * X + Oxide % in Limestone. – Oxide% in Limestone * X = Oxide % D * X + oxide % in Limestone D: Differentiated ratio between oxide in clay and Limestone (oxide % in clay – oxide % in Limestone) with constant LSF. If MgO ≤ 2% LSF = 100 (CaO% + 0.75 MgO %) / 2.8 SiO2 % +1.2 A12O3 % + 0.65 Fe2O3 %

LSF = 100 (CaO%D * X + CaO%L + 0.75 MgO%D * X + 0.75 MgO%L) / 2.8 SiO2%D * X + 2.8 SiO2%L + 1.2 A12O3%D * X + 1.2 A12O3%L + 0.65 Fe2O3%D * X + 0.65 Fe2O3%L. LSF [X (2.8 SiO2%D + 1.2 A12O3%D + 0.65 Fe2O3%D) + (2.8 SiO2%L, + 1.2 A12O3%L + 0.65 Fe2O3%L)] = 100 [X (CaO%D + 0.75 MgO%D) + (CaO%L +0.75 MgO%L)]. X * LSF (2.8 SiO2%D + 1.2 A12O3%D + 0.6 Fe2O3%D) - X * 100 (CaO%D + 0.75 MgO%D) = 100 (CaO%L + 0.75 MgO%L) – [LSF (2.8 SiO2%L, + 1.2 A12O3%L + 0.65 Fe2O3%L)] X = 100 (CaO%L +0.75 MgO%L) - LSF (2.8 SiO2%L, + 1.2 A12O3%L + 0.65 Fe2O3%L) / LSF (2.8 SiO2%D + 1.2 A12O3%D + 0.65 Fe2O3%D) – 100 (CaO%D + 0.75MgO%D) So... Clay % = X and then Limestone % = l-X The result shows the percentage of clay in the mixture, and subtracted by one which produces a percentage of limestone. As an example for these calculations, limestone A1 with clay C1 are taken as shown in the table (3-9).The compensation values of the above-mentioned basic oxides in the previous equation produce: X= 100*(55.15 + 0.75 *0.37)-90*(2.8*0.17 + 1.2*0.23 + 0.65*0.05)/90*(2.8*42.27 + 1.2*11 + 0.65*6.27)-100*(-40.21 + 0.75*2.32) X=0.33 Y= 1-X 72

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=1-0.33 = 0.67 Not: In this study, the LSF value was fixed on 90 and 95 for calculating the proportion of raw materials in the mixture. Table (3-10): Summary of practical steps to calculate the composition of the mixture and clinker expected with some properties

Oxide SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O L.O.I ToTal

Bn2 0.17 0.23 0.05 55.15 0.37 0.07 0.00 0.03 43.68 99.75

C1 Re.cast C1 D 42.20 42.44 42.27 11.17 11.23 11.00 6.28 6.32 6.27 14.86 14.94 -40.21 2.67 2.69 2.32 0.03 0.03 -0.04 0.14 0.14 0.14 0.98 0.99 0.96 21.25 21.37 -22.31 99.44 100.00

LSF*= LSF calculated

Bn2*Y 0.11 0.15 0.03 37.12 0.25 0.05 0.00 0.02 29.40

C1*X 13.88 3.67 2.07 4.89 0.88 0.01 0.05 0.32 6.99

Mixture Clinker 13.99 22.04 3.83 6.03 2.10 3.31 42.00 66.15 1.13 1.78 0.06 0.09 0.05 0.07 0.34 0.54 36.38 99.88 100.00

Clinker ratio, Proportion Phase and Properties LSF* 94.93 LSF** 95.00 SR 2.36 AR 1.82 C3S 56.35 C2S 20.67 C3A 9.85 C4AF 10.06 H.M 2.11 M.B.T 1307.46 B.I 2.83 L.Ph. 28.00

LSF**=LSF assumed95

3.3.2. Clinker production 3.3.2.1. Theoretical chemical composition of clinker After determining the proportion of the mixture contribution of clay and limestone which are 33% and 67% respectively, the chemical composition of the final mixture is calculated by finding the proportion of each oxide from both clay and limestone by multiplying the Concentration of each oxide in the clay by 0.33 and the oxide in the limestone by 0.67 as shown in the fields (C1*X), (Bn2*Y) of (Table 3-10). Then the concentration of each oxide in the final mixture is obtained by the sum of these two fields (Table 3-10). The next step is to find the expected chemical composition of the clinker. Taking into account, that the clinker has no loss due to burning, (L.O.I) for the clinker is equal to zero and then the process of re-calculation is conducted for all the remaining oxides in the mixture at the absence of (L.O.I) so as to obtain the expected percentage of each oxide in the clinker.

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3.3.2.2. Calculation clinker parameters (Ratio) In order to ensure the clinker quality, the following composition parameters (moduli) are controlled (LSF, SR and AR). When comparing chemical analysis of Portland cement (feed raw materials/ or clinker), it was found that certain relations exist between the percentage of lime on the one hand and the combination of silica, alumina and iron oxide on the other (Aldieb & Ibrahim.,2010 and Alemayehau & Sahu, 2013). These parameters (modulus) are:

3.3.2.2.1. Limestone saturation factor (LSF) It is the ratio of the actual amount of lime to the theoretical lime required by the other major oxides in the raw mix or clinker, when LSF>100% the ordinary clinker always contains some free lime (Alemayehau and Sahu , 2013). This free lime changed to hydroxide with time then to carbonate, and enlarged the volume, thus leads to the expansion of the concrete and fracturing. The LSF is used for kiln feed control; a higher LSF makes it difficult to burn raw mix (Rao, et al., 2011). To monitor the burning process, the amount of unreacted CaO, free in the clinker, is analysed. The lower the free lime closer the reactions are to completion however, too low free lime can also indicate too hard

and uneconomic burning. The free lime target is normally about 0.5 to 1.5% CaO free (Fasil Alemageha, et al., 2013). A high LSF also requires high heat consumption for clinker burning inside the kiln thus gives more strength to the cement but that means more fuel consumption which leads to high cost of production and damages to the kiln walls (Al-Auweidy, et al, 2013). The LSF controls the ratio of alite to belite in the clinker, a clinker with a higher LSF will have higher proportion of alite C₃S to belite C₂S than clinker with low LSF (RaO, et al., 2011). LSF (MgO ≤ 2%) = 100 (CaO + 0.75 MgO) / 2.8 SiO₂ + 1.2Al₂O₃ + 0.65 Fe₂O₃) LSF (MgO ≥ 2%) = 100 (CaO + 1.5 MgO) / 2.8 SiO₂ + 1.2Al₂O₃ + 0.65 Fe₂O₃)

Rao, et al believes that if the values are above 100%, it indicates that free lime is likely to be present in the clinker. This is because, in principle, at LSF =100 all the free lime should have combined with belite to form alite. Moreover, the normal range of LSF is 90-98%, but if it is 80% it does not create any problem in cement manufacturing process 74

Chapter three

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and cement strength but should not go below this range (Amin and Ali., 2010). According to BS 12-78 the value of LSF is about 66 -102, but in Iraq most cement factories depended on the LSF value which is between 90 -100. The LSF in the studied samples ranges between (89.84- 91.26) and (94.47- 95.25) when LSF is equal 90 and 95 respectively (Appendix. D and E) and this indicate that all the studied samples are in an acceptable range.

3.3.2.2.2. Silica Ratio The silica ratio is sometimes called silica modulus. The SR has especially great influence on burning process and on some cement features (Rao, et al., 2011). It is the proportion of SiO₂ to the total of Al₂O₃ and Fe₂O₃ given as following: SR = SiO₂/Al₂O₃ + Fe₂O₃ When SR is increased the amount of liquid phase is decreased and vice versa (Fundal, 1980 in Khalid, 2006). So SR has a major influence on the formation of liquid phase (De Schepper, et al., 2011). The SR also affects the grindability of clinker, when there is more liquid phase which means that SR is low and this it causes the lower grindability of the clinker (Tokyay, 1998). Liquid phase = 71 / 0.53 + SR……. (Fundal, 1980) When the SR increased the formation of nodules and the chemical reactions may be too slow making it difficult to operate and it is harder to burn (Alemayehau and Sahu, 2013). This causes slow setting and hardening of the cement, high strength of cement is obtained (Aldieb and Ibrahim, 2010). Moreover, increasing SR means that more Calcium silicate (Alite and Belite) are present in the clinker and less aluminate and ferrites (Rao, et al., 2011) and leads to deteriorate the kiln lining (Ghosh, 1991 in: Al-Aweidy, 2013). When SR is too decrease there may be too much liquid phase and the sulphur coating can become too thick (Alemayehu and Sahu , 2013). Also low SR leads to formation ring in the cement (Rao, et al., 2011). Generally, SR ranges between 1.9-3.2% according to (Aldieb and Ibrahim, 2010), between 2.0-3.0% according to (Rao, et al., 2011) and 2.1±0.1 % according to

75

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(Alemayehau and Sahu, 2013).Large variation of SR in the clinker can be an indication of poor uniformity in the kiln feed. The SR in the studied samples ranges between (1.56- 3.48) and (1.55- 3.47) when LSF is equal to 90 and 95 respectively (Appendix. D and E),and this indicates that the studied samples are in agreement with acceptable range, except those mixtures that are created with clay sample C4 in Banishar area and their SR is out of range.

3.3.2.2.3. Alumina ratio AR or Alumina Modulus AM The alumina ratio is characterizing the cement by the proportion of alumina to iron oxide; given as following: AR = Al₂O₃ / Fe₂O₃ This determines the potential relative proportions of aluminate and ferrite phase in the clinker (Rao, et al., 2011). An increase in clinker AR means there will be proportionally more aluminate and less ferrite in the clinker (Rao, et al., 2011).The values AR is in the range from 1.5-2.5% according to (Aldieb and Ibrahim, 2010), the AR determines the composition of liquid phase in the clinker, when the range is lower than 1.5% both oxides are present in their molecular ratios and therefore only C₄AF can be formed in the clinker. Consequently, the clinker cannot contain tricalcium aluminate and this case is called Ferrari-cement which is characterized by low heat of hydration, slow setting and low shrinking (Aldieb and Ibrahim, 2010). A higher AR together with low SR results, among other things, in fast setting of the cement; this requires the addition of higher gypsum rate to control the setting time. The AR only has a significant effect on clinker formation at low temperature (De Shepper, et all, 2011). Also the AR affects the colour of clinker and cement, the higher AR the lighter the colour of cement (Alemayehau and Sahu, et al., 2013), according to this author AR range is equal 1.2 ± 0.2%.But in general the AR in ordinary Portland cement clinker is usually between 1.0 and 4.0 (RaO, 2011). The AR in the studied samples ranges between (1.05- 1.82) and (1.04- 1.82), when LSF is equal to 90 and 95 respectively (Appendix. D and E). This indicates that all the studied samples are in agreement with acceptable ranges. From the above study, it was concluded that cement module Lime saturation factor (LSF), Silica ratio (SR) and Alumina ratio (AR) on the limit from all four section Appendix (D and E) except few sample which are out of the limit. Variation clinker quality 76

Chapter three

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can be decreased by carrying out various steps at different levels which reduce the deviation of blending efficiency, raw mill feed, kiln feed and clinker compositions and its minerals. These ratios are control by raw mill process and kiln process ( Alemayehu and Sahu, 2013).

3.3.2.3. Clinker phase Main constituent phases of Portland cement clinker: The properties of Portland cement are mainly determined by the proportion of its four principle clinker phases which are the impure forms of Ca₃SiO5 (alite), Ca₂SiO₄ (belite), Ca₃Al₂O6 (tricalcium aluminate) and C₄AF (tetracalcium aluminate ferrite). Other phases such as periclase (MgO), quartz (SiO₂), free lime (CaO), etc. may also be present in minor quantities, usually less than 1%w. The clinker quality is affected by these phases, the burnability becomes worse as C₃S content increase while in increasing C₃A and C₄AF, the burnability improves (Ghosh, 1983 In: Dutta, 2011).

3.3.2.3.1. Alite C₃S Alite is the most important constituent clinker component and typically constitutes 38-60% in normal Portland cement (Brandt, 2009). It is tricalcium silicate modified in composition and crystal structure by ionic substitutions (Aldieb and Ibrahim, 2010); it is produced by chemical reaction between CaO and SiO₂. C₃S contributes to early strength of cement and it is resistant to sulphur attack, high content of C₃S will increase strength of clinker and cement at all ages (Alemayehau and Sahu, 2013). C₃S is stable between about 1250°-1800° and melt congruently at 2150° (Bye, 1999).C₃S hardens quickly with evolution of heat and gives early strength (Guirguis, 1998). Mostly alite in a clinker phase is formed between 1250°-1450° (Telschow, 2012), and liquid phase is formed at this temperature. Chemical reactions for clinker formation at various temperatures are illustrated in (Fig, 3-1). The C₃S in the studied samples range between (38.08-57.67) and (50.71-69.70) when LSF is equal to 90 and 95 respectively, see appendix D and E. Comparing this result with typical constituents of C₃S in normal Portland cement (Brand, 2009) it becomes clear that the C₃S content of all the studied samples is within the range except a few samples which are out of this range, see appendix D and E.

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3.3.2.3.2. Belite C₂S The second major constituent phase of Portland clinkers is the impure form of dicalcium silicate. Its content in Portland clinkers is typically 15-38% (Brandt, 2009). Reaction between CaO and SiO₂ will produce belite. It is also responsible for the strength of Portland cement ; high percentage of C₃S (low C₂S) results in high strength, but also high heat generation as the concrete sets , the reverse combination of low C₃S and high C₂S develops strength and generates less heat (Rao, et al., 2011). According to Guirguil (1998), C₂S hardens slowly and gives late strength. This phase is formed at temperature 900°-1250° (Telschow, 2012). It represents higher stability at low temperature than C₃S (Taylor, 1992 in: TenÓrio and Pereira, 2005). The C₂S in the studied samples ranges between (26.67-32.94) and (16.08-21.43) when LSF is equal to 90 and 95 respectively, appendix D and E. The C₂S content of the studied samples, according to Brandt, (2009) has acceptable range (Table 3-11).

3.3.2.3.3. Aluminate C₃A It is the most reactive component of Portland cement clinker which contains 7-15 % of the phase (Brandt, 2009). Reaction between CaO and Al₂O₃ will produce aluminate, which is substantially modified composition and sometimes structured by ionic substitutions (Aldieb and Ibrahim, 2010). The presence of C₃A in cement is undesirable (Amin and Ali, 2010).This phase is formed at temperature 900°-1250° (Telschow, 2012). This phase sets quickly with evolution of heat and enhances strength of the silicates (Guirguis, 1998). The C3A in the studied samples ranges between (6.03-11.00) and (5.3010.45) when LSF is equal to 90 and 95 respectively, shown in appendix D and E. This indicates that all the studied samples are in agreement with typical constituent of normal Portland cement by Newman, (2003) and Brandt, (2009),Table 3-11, except a few samples % which are less than this range Appendix D and E.

3.3.2.3.4. Ferrite C₄AF The average composition and constituents is about 6-18 % of typically clinker (Brandt, 2009). Reaction between CaO-Al₂O₃-Fe₂O₃ will produce ferrite. C₄AF is substantially modified in composition by variation in AL/Fe ratio and ionic substitution 78

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(Aldieb and Ibrahim, 2010). It reduces the clinkering temperature and acts as flux in burning the clinker. It hydrates rather rapidly but contributes very little strength. C₄AF is also present in cement in small quantities, and if compared with other three phases it does not affect the behaviour of the cement significantly (Bye, 1999 In: Amin and Ali, 2010). It has little cementing value (Guirguis, 1998). This phase is formed at temperature 900°-1250° (Telschow, 2012). The C₄AF in the studied samples ranges between (6.4520.03) and (6.22-19.51) when LSF is equal to 90 and 95 respectively (appendix D and E).This indicates that all the studied samples are in acceptable range. If compared with mineralogical composition % in Portland cement by Newman, (2003) and Brandt, (2009) (Table 3-11), but except few samples are more than this range (appendix D and E). In addition theoretical phase compositions were predicted by using a modified Bogue calculation (Lin and Lin, 2006) as shown below: A- If: Al₂O₃ / Fe₂O₃ (alumina ratio) >0.64 the clinker phases calculated as: C₃S = 4.071 CaO – (7.602 SiO₂ + 6.718 Al₂O₃ + 1.43 Fe₂O₃ + 2.852 SO₃) C₂S = 2.867 SiO₂ - 0.7544 C₃S C₃A = 2.650 Al₂O₃ - 1.692 Fe₂O₃ C₄AF = 3.043 Fe₂O₃

B- If: Al₂O₃ / Fe₂O₃ (alumina ratio) <0.64 the clinker phases predicted by these equations. C₃S = 4.071 CaO – (7.602 SiO₂ + 4.479 Al₂O₃ + 2.859 Fe₂O₃ + 2.852 SO₃) C₂S = 2.867 SiO₂ - 0.7544 C₃S C₃A = 0 C₄AF- C₂F = 2.100 Al₂O₃ -1.702 Fe₂O₃ After studying all the sections, the AR is more than 0.64; so the equations A were used for calculation of the four major phases.

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Table (3-11): Mineralogical composition percent Portland cement, (after Newman, 2003 and Brandt, 2009).

Cement

Mineral

Typical level

Typical range

notation

name

(Mass %)

(Mass %)

composition

C₃S

Alite

57

38- 60

3CaO. SiO₂

C₂S

Belite

16

15- 38

2CaO. SiO₂

C₃A

Aluminate

9

7- 15

3CaO. Al₂O₃

C₄AF

Ferrite

10

6- 18

4CaO. Al₂O₃. Fe₂O₃

Chemical

Figure.3.3.Schematic illustrations of the typical proportions of phases for the formation of Portland clinker minerals as a function of the progressive kiln temperature. The figure is adapted from the (Hewlett, 1998) in (Aldieb and Ibrahim, 2010). 80

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3.3.2.4. Clinker properties Some important properties of clinker were calculated using Bogue (1955), these properties include

3.3.2.4.1. Hydraulic modulus (HM) It is generally limited by the values 1.7-2.3 (Aldieb and Ibrahim, 2010), and it has the following form: HM = CaO / SiO₂ + Al₂O₃ + Fe₂O₃ It was found that with an increasing HM, more heat is required for clinker burning, the strength, especially the initial strength set up, and also the heat hydration rises, and simultaneously the resistance to chemical attack decreases (Rao, et al., 2011). Generally cement with HM lesser than 1.7 showed mostly insufficient strength; cement with HM greater than 2.3 had poor stability of volume; hence, the clinker of the studied samples HM it ranges between (1.82-2.19) and (1.91-2.31) when LSF is equal to 90 and 95 respectively, Appendix D and E. This means that all the studied samples have acceptable range of HM.

3.3.2.4.2. Minimum burning temperature (MBT) The MBT is represents the degree, in which the liquid phase to be, begins appear in the Furnace, and depends on the ratio of (Al₂O₃, Fe₂O₃) in the raw mix, but (Fe₂O₃) has greater effect. The proportion of lime and silica causes augmentation in value. Which is better not to be less than (1250°C), since only after this temperature (C₃S) is begins to appear (Chatterjee, 1979).The MBT can be calculated by the following equation: MBT°C = 1330 + 4.51 * C₃S – 3.74 *C₃A – 12.64 * C₄AF

The MBT of clinker in the studied samples ranges between (1230.73°-1486.95°) and (1207.79°-1544.20°) when LSF is equal to 90 and 95 respectively, appendix D and E. This means that all the studied samples have acceptable range of MBT.

3.3.2.4.3. Burnability Index (B.I) The burnability index is expressed as the percentage between the phase (C₃S) to total phases (C₃A + C₄AF) as follows: B.I = C₃S / C₃A + C₄AF

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Susceptibility depends on the chemical composition of the burning mixture of raw mix, since any change in the composition leads to a change in susceptibility burning, the rate of B.I in cement ranging between (2.6- 4.5) (Yezdeen , 1990) and (Peray and Waddell, 1972, In: Al-Ali, 2001). This ratio has good susceptibility burning. The B.I of clinker of the studied samples ranges between (1.44 -4.74) and (1.95-5.91) when LSF is equal to 90 and 95 respectively, appendix D and E. This indicates that some samples are out of this range.

3.3.2.4.4. Liquid phase at the burning zone It is the amount of liquid formed at a temperature of formation of clinker, and depends on the firing temperature and chemical composition of the mixture, as well as on the proportion of each of (Al₂O₃, Fe₂O₃, MgO, K₂O, Na₂O).It works as helping material to the fusion which leads to the rise in the proportion of the liquid phase of the burning process and the formation of phases of clinker. The liquid phase of the studied samples was calculated from the formula proposed by Lea- Parker in Gouda (1979) as:

Liquid phase (L.Ph) % = 3.0 Al₂O₃ +2.25 Fe₂O₃ + MgO + K₂O + Na₂O +SO₃ (1450C°)

The acceptable ranges of L.ph in cement clinker at temperature 1450C° ranging between 23% to 27% (Peray and Waddell, 1972). The cement clinker of the studied samples ranges between 17.13 to 38.20 and 16.57 to 37.09when LSF is equal to 90 and 95 respectively (Appendix D and E ). Accordingly, most the studied samples have not acceptable values according to (Peray and Waddell, 1972) except few samples within this range. To reduce the liquid phase, SR must be increased by adding higher amount of sand to the mixture because sand is the main source for SiO₂.

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CHAPTER FOUR PHYSICAL AND MECHANICAL PROPERTIES OF RAW MATERIALS 4.1. Preface In addition to assessment of chemical and mineralogical characteristic an evaluation of limestone for cement industry must also consider certain physical and mechanical properties of the stone. Strength is of prime importance in assessment for cement use, together with other properties such as apparent porosity, water absorption, bulk density, apparent specific gravity and natural moisture content. These properties and particle size distribution of the soil samples are important properties in the evaluation of the raw materials used in cement industry. For this purpose all the limestone and soil samples were studied physically and mechanically.

4.2 Physical properties Determining the physical properties of limestone of Avroman Formation such as apparent porosity, bulk density, apparent specific gravity, water absorption and natural moisture content were established on 46 samples using the procedure described by IQS standard No.31 (1981) in appendix (F). Physical properties of rock were influenced by internal geometry of the rock such as grain size, pore size, grain shape, pore connectivity, fracture geometry, orientation structure and texture (SchÖn, 2011).

4.2.1 Apparent porosity Apparent porosity otherwise called effective or net porosity, is a measure of the interconnected void space which communicates with the surface of the test specimen, it therefore does not include the sealed-off or occluded pores (Manger, 1963).Apparent porosity is obtained by determining the fluid capacity of the interconnected pore, that is the pore volume (VP) and by dividing this volume by the bulk volume (VB) (Manger, 1963). The equation for apparent porosity (PA) by percent is: PA ={VP /VB } *100

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The apparent porosity (PA) of the test specimen is defined as P% = {(M – D)/ (M- S)}*100 P: Apparent porosity in % M: saturated weight in gm D: dry weight in gm S: suspended weight in gm The Porosity character depends on the size, shape, crystal system, grading, packing and binding materials (cementitous materials) of particle (Khalid, 2006) and (Hussein, 2011 and 2012). Khalid(2006) mentioned that the porosity of organic rocks and rocks have medium purity greater than crystallized limestone. Table 4-1 displays that all the studied samples have apparent porosity ranges between (1.1-7.9) % except samplesBn10 and H7which are 10.29 and 13.22 % respectively. The apparent porosity has inverse relationship with compressive strength. So increasing the pore volume or open space in the rock needs less strength for the sample until it fails and vice versa. In Ahmad Awa section, the porosity ranges between (1.83-4.56) percent which means the rock in this section has slightly low porosity which means that it is hard because when porosity decreases the resistance of rock increases and vice versa. But in Shanaw valley section (Sh) the porosity ranges between (1.92-6.19) percent. In this section the samples have slightly a porosity value similar to the world standard specification (Table 42). In Banishar valley section (Bn) the porosity increases if compared to other sections the limestone samples in this section are soft and they contain vugy porosity in some locations which indicate that the porosity in this section is high if compared to other sections and the range porosity is between (1.64-7.9) percent except Bn10 which reached 10.29%. While in Helanpe section (H) the porosity, like the other sections is not very high and it is less than the Banishar valley section; the range porosity is between (1.10-5.06) percent except (H7) which reached 13.22%. The results of apparent porosity percentage of the Avroman limestone Formation is slightly or nearly in the range of world standard specification Chatterjee (2004) for physical and mechanical properties of limestone (Table 4-2). This indicates that the rock are needs suitable force for crushing if used for manufacturing Portland cement because when porosity is very low, more loading is needed for crushing or extraction in quarry. 84

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Table (4-1): Physical properties of limestone Avroman Formation of the studied samples. Sample No. A1 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 Sh1 Sh2 Sh4 Sh5 Sh6 Sh7 Sh8 Sh9 Sh10 Sh11 Sh12 H1 H2 H3 H4 H5 H6 H7 H8 H9 H11 Bn1 Bn2 Bn3 Bn4 Bn5 Bn6 Bn7 Bn8 Bn9 Bn10

Apparent Porosity % Bulk Density gm/cmᶟ Apparent SPG gm/cmᶟ Water absorption% Natural Moisture content % 2.35 2.60 2.66 0.90 0.0055 2.13 2.64 2.69 0.81 0.0040 3.00 2.61 2.69 1.15 0.0092 3.51 2.62 2.71 1.34 0.0182 4.56 2.61 2.73 1.75 0.0181 4.14 2.65 2.77 1.56 0.0135 3.27 2.60 2.69 1.26 0.0131 3.10 2.60 2.69 1.19 0.0110 2.52 2.65 2.72 0.95 0.0132 2.63 2.63 2.70 1.00 0.0206 1.82 2.65 2.70 0.69 0.0063 3.27 2.64 2.73 1.24 0.0113 1.87 2.68 2.73 0.70 0.0124 3.09 2.66 2.75 1.16 0.0160 3.49 2.58 2.68 1.35 0.0157 5.16 2.47 2.60 2.09 0.0353 3.68 2.53 2.62 1.46 0.0250 3.86 2.55 2.66 1.51 0.0003 6.19 2.41 2.57 2.56 0.0895 3.12 2.55 2.63 1.22 0.0407 4.57 2.52 2.64 1.81 0.0051 3.22 2.56 2.65 1.26 0.0554 3.47 2.55 2.65 1.36 0.0028 1.91 2.60 2.65 0.74 0.0057 2.52 2.59 2.66 0.97 0.0190 4.52 2.51 2.63 1.80 0.0110 3.26 2.63 2.72 1.24 0.0278 2.34 2.54 2.60 0.92 0.1090 5.06 2.57 2.71 1.97 0.0069 1.37 2.63 2.67 0.52 0.0014 2.89 2.61 2.69 1.11 0.0058 2.29 2.60 2.67 0.88 0.0066 13.22 2.25 2.60 5.87 0.0288 3.78 2.50 2.60 1.51 0.0634 1.10 2.67 2.70 0.41 0.0059 2.80 2.52 2.59 1.11 0.0311 2.11 2.65 2.71 0.80 0.0141 7.78 2.49 2.70 3.13 0.0376 7.90 2.41 2.62 3.28 0.0708 3.81 2.56 2.66 1.49 0.0093 4.48 2.57 2.69 1.75 0.0082 1.64 2.66 2.70 0.62 0.0051 6.70 2.42 2.60 2.76 0.0073 4.15 2.54 2.65 1.63 0.0064 2.03 2.65 2.70 0.77 0.0030 10.29 2.40 2.67 4.29 0.0029

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4.2.2. Bulk density The bulk density of specimen is the quotient of its dry weight divided by the exterior volume including pores (Bulk volume) (Aurangzeb, 2009). ρ = D/ V The bulk density of the test specimen is defined as: ρ = {D/ M-S} * γ Where: ρ: Bulk density gm/Cmᶟ D: dry weight in gm M: saturated weight in gm S: suspended weight in gm Table (4.1) displays the results of bulk density of studied samples range between (2.25-2.68) gm/ cmᶟ. The results of bulk density values (Table 4-1) of the studied samples are more than the acceptable range described by Chatterjee (2004) (Table 4-2). Bulk density of rock depends on the mineral composition (mineral densities and volume fractions), porosity (pores and fractures) and density of pore fluids (SchÖn, 2011). The relationship between bulk density and apparent porosity is reversal (Fig.4.1 A). Density and porosity often related to the strength of rock material; a low density and high porosity rock usually has low strength. When the bulk density increases, it means that the grains connected and more compacted which causes the decrease of apparent porosity decrease. In this case, more energy is needed for crushing and grinding when evaluation is made for the rock sample for manufacturing Portland cement or cement industry. Table (4-2): Physical and mechanical properties of some limestone rocks (Chatterjee, 2004).

Sample No. 1 2 3 4 5

porosity% 4.03 6.16 2.51 3.73 4.45

Total density Apparent specific compressive strength (gm/cmᶟ) gravity (gm/cmᶟ) (Kg/cmᶟ) 1.63 2.73 852.44 1.67 2.72 458.81 1.41 2.63 1242.30 1.44 2.66 1414.00 1.65 2.7 484.80 86

Chapter four

Physical & Mechanical Properties of Raw materials

4.2.3. Apparent specific gravity It is the ratio of the weight in air of a unit volume of a permeable material (including all voids) to the weight in air (of an equal density) of an equal volume of gass free distilled water (Aurangzeb, 2009). The apparent specific gravity (T) of the test specimen is defined as: T= {D/ (D- S)} * γ Where: T: apparent specific gravity gm/cmᶟ D: dry weight in gm S: suspended weight in gm γ: density of water gm/ cmᶟ The apparent specific gravity value of the studied samples (4-1) ranges between (2.57- 2.73) gm/cmᶟ which is nearly similar to the standard world specification of limestone described by Chatterjee (2004) (Table 4-2). It means that all the samples have acceptable range of apparent specific gravity.

4.2.4. Water absorption It is the weight of water absorbed by the sample after 24 hours of immersion in water divided by its oven – dried weight expressed as percentage of (Mohd, 2002), and expressed as such: Water absorption (A) % = {(M-D) / D} * 100 Where: A: water absorption % M: saturated weight in gm D:dry weight in gm

Table (4-1) displays the water absorption results of the studied samples ranges between (0.41 – 5.87) %. When apparent porosity increases, the water absorption increases and vice versa. Water absorption has strong positive correlation with apparent porosity (Fig 4.1 B).

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4.2.5. Natural moisture content Moisture (water) content by mass of material is the ratio of the mass of water contained in the pore spaces of soil or rock material, to the solid mass particles in that material, expressed as a percentage (ASTM. D2216-2010), a standard temperature of 110± 5°C is used to determine these masses.

Moisture content = {Mw / Ms} *100 Where: Mw: mass of water in gm Ms: mass oven dry spacemen in gm The natural moisture content W% of the test specimen is defined as: W% = { Mw / Ms } * 100 Mw = mass of sample before drying in oven – mass of sample after oven drying.

Table (4-1) represents the results of moisture content for the studied samples. The moisture content in Ahmad Awa section ranges between 0.004 to 0.0206 % and in Shanaw valley section it ranges between 0.0003 to 0.0895 %, while in Helanpe and Banishar valley sections it ranges between 0.0014 to 0.1090 % and 0.0029 to 0.0708 % respectively. The moisture content is considered as a factor that makes limestone rocks suitable for cement industry because this property has direct relationship with required energy for drying the mixture during manufacturing process. For relatively high moisture in raw materials and for start-up procedure, an auxiliary furnace may be needed to provide additional heat for drying (CEMBUREAU-1999).

The natural moisture content of raw materials has a

significant impact on the operations of the creation of such materials and the processes (wet or dry) as well as its role in energy consumption (Khalid, 2006).The choice of the process is mainly based on the nature of the available raw materials. When the moisture content in raw materials is more than 20% and up to 45%, the wet method is preferred to the dry method (ETSAP-2010), but to save energy the wet process moves to dry process as it consume less energy compared to wet process (Madool, et al., 2011), but it needs more grinding than the wet process.

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2.75 2.70 R² = 0.7754

2.65 Bulk density gm/cmᶟ

2.60 2.55 2.50 2.45 2.40 2.35 2.30 2.25 2.20 0.00

2.00

A-

4.00

6.00

8.00

10.00

12.00

14.00

Apparent Porosity %

7.00

R² = 0.9968

Water absorption %

6.00 5.00 4.00 3.00 2.00 1.00 0.00 0.00

B-

2.00

4.00

6.00

8.00

10.00

12.00

14.00

Apparent Prosity %

Figure (4.1): linear relationship between Apparent porosity and (A- Bulk density, and B- water absorption) of the studied samples.

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4.3. Mechanical properties (Uniaxial compressive strength UCS) of limestone Compressive strength measures the failure point and it is defined as many forces including internal cohesion between grains and crystal with external force that is perpendicular on the sample (Fatuhy, et.al., 1981 in: Hussein, 2010).Itis used to define the failure point at rock sample during size reduction where the sample is loaded. For this test the point load index is used and correlated to the uniaxial compressive strength (UCS). The procedure for measuring the rock compressive strength has been standarized by both international society for rock mechanics (ISRM -1981) and (ASTM 1984). The method is time consuming and expensive as it requires specimen preparation (Akram and Bakar, 2007). Indirect tests such as point load index (IS50) are used to predict the UCS. These tests are easier to carry out because they necessitate less or no sample preparation, and testing equipment is less sophisticated, also they can be used easily in the field (Akram and Bakar, 2007). The test was performed according to the procedure of ISRM (1985), in which the point load strength allows the determination of the uncorrected point load strength index (Is), shown in appendix (G). The UCS test is adopted for 46 samples of limestone by using point load apparatus (ELE-model) in the Engineering Laboratory of University of Sulaimani. This test is used for different diameter sample (Appendix G) and the results are shown in (Table 4-3). The value of UCS for each sample was determined, then the rocks were classified depending on Anon (1972) (Table 4-4). Most of the limestone contains cementitous materials (binding materials) which could affect the resistance. The resistance of the rock increases by increasing this material. Compressive strength of limestone for crushing depends on impurity, degree of crystallization, nature of cementitous material, porosity, moisture content and the grade of natural weathering that has effects on the rock (Neville, 1981). The high degree of crystallization in limestone has more compressive strength than low degree of crystallization. Extraction method also depends on the hardness of the rocks; for example, mining chalk and claystone can be extracted from the face of the quarry without having to blow up, but the limestone rocks with high hardness and high purity need to blow the quarry and to crush more than one before milling and transferring to mixing unit (Bye, 90

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1983 in: Khalid, 2006). The compressive strength of limestone for cement industry must be less than (950 – 1000) kg/cmᶟ Chatterjee(1979), but according to standard world the range of compressive strength of limestone (Chatterjee, 2004) is between (458.81-1414.0) Kg/cmᶟ (Table 4.2). The results of UCS value for studied samples (Table 4-3) in A-section range between (742-1405) Kg/cmᶟ, which are in agreement with standard range of international world range of limestone (Table 4-2). While in Shanaw valley (Sh) section the UCS ranges between (674-1484) Kg/cmᶟ;the compressive strength of the samples in this section is similar to A-section. Moreover, other sections such as Helanpe (H) and Banishar valley (Bn) have compressive strength which is less than the A and Sh sections, and ranges between (405-1502) Kg/cmᶟ in H-section and (200-1464) Kg/cmᶟ in Bnsection. The increasing and decreasing of compressive strength are related to the porosity that is present in the samples; if the strength increases, the porosity decreases and vice versa. Moreover the joint and fracture are important factors that affected the compressive strength of this rock. From above results, it can be conclude that the processes of crushing and grinding need a suitable force (energy) during the extraction of a sample in the quarry.

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Table (4-3): Steps for finding uniaxial compressive strength (UCS) of limestone samples for each studied section. Sample No. A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 Sh1 Sh2 Sh3 Sh4 Sh6 Sh7 Sh8 Sh9 Sh10 Sh11 Sh12 Sh13 H1 H2 H3 H4 H5 H6 H8 H9 H10 H11 Bn1 Bn2 Bn3 Bn4 Bn6 Bn7 Bn8 Bn9 Bn10

P (KN) 8.50 13.00 8.50 6.50 16.00 6.00 6.50 7.00 7.00 5.50 6.00 13.50 6.50 7.00 6.50 8.50 6.00 7.50 8.00 10.00 8.50 5.00 5.00 11.00 7.50 6.50 7.50 7.20 7.00 4.80 7.50 7.50 7.00 3.00 7.50 9.00 7.00 10.20 5.24 6.20 7.50 5.00 1.60 10.00 6.00 1.50

De (mm) 39.00 45.00 39.00 39.00 52.00 39.00 39.00 33.00 38.00 39.00 39.00 47.00 41.00 39.00 41.00 35.00 39.00 39.00 39.00 43.00 39.00 39.00 39.00 39.00 35.00 39.00 39.00 39.00 39.00 39.00 39.00 36.00 39.00 39.00 39.00 34.00 37.00 39.00 36.00 39.00 39.00 32.00 39.00 37.00 39.00 39.00

Is =p/De² (MN/m²) 5.59 6.42 5.59 4.27 5.92 3.94 4.27 6.43 4.85 3.62 3.94 6.11 3.87 4.60 3.87 6.94 3.94 4.93 5.26 5.41 5.59 3.29 3.29 7.23 6.12 4.27 4.93 4.73 4.60 3.16 4.93 5.79 4.60 1.97 4.93 7.79 5.11 6.71 4.04 4.08 4.93 4.88 1.05 7.30 3.94 0.99

Is50 = F*Is (Mn/m²) F=(De/50)^0.45 5.00 6.12 5.00 3.82 6.02 3.53 3.82 5.33 4.28 3.23 3.53 5.94 3.54 4.12 3.54 5.91 3.53 4.41 4.70 5.05 5.00 2.94 2.94 6.47 5.21 3.82 4.41 4.23 4.12 2.82 4.41 4.99 4.12 1.76 4.41 6.55 4.47 6.00 3.49 3.65 4.41 3.99 0.94 6.38 3.53 0.88

92

UNS (Mpa) UNS=22.5*Is50 112 138 112 86 136 79 86 120 96 73 79 134 80 93 80 133 79 99 106 114 112 66 66 146 117 86 99 95 93 63 99 112 93 40 99 147 100 135 78 82 99 90 21 144 79 20

UNS (Kg/cm²) Classification (depending on Anon,1972) 1147 Very strong 1405 Very strong 1147 Very strong 877 Strong 1382 Very strong 809 Strong 877 Strong 1223 Very strong 983 strong 742 Strong 809 Strong 1364 Very strong 811 Strong 944 Strong 811 Strong 1356 Very strong 809 strong 1012 strong 1079 Very strong 1159 Very strong 1147 Very strong 674 strong 674 strong 1484 Very strong 1196 Very strong 877 strong 1012 strong 971 strong 944 strong 647 strong 1012 strong 1145 Very strong 944 strong 405 Moderately strong 1012 strong 1502 Very strong 1024 Very strong 1376 Very strong 800 strong 836 strong 1012 strong 916 strong 216 Moderately strong 1464 Very strong 809 strong 200 Moderately strong

Chapter four

Physical & Mechanical Properties of Raw materials

Table (4-4): Point load strength classification (After Anon, 1972) Term Extremely strong Very strong Strong Moderately strong Moderately weak Weak very weak

Point load strength index(MN/m²) >12 6-12

Equivalent uniaxial compressive strength(MN/m²) Over 200 100-200

3-6 0.75-3 0.3-0.75 0.075-0.3 <0.075

50-100 12.5-50 5-12.5 1.25-5 <1.25

4.4. Texture Analysis of the studied Soil: The proposed method was followed by (Standard Test Method for Particle-size of Soils D422-63, 2002). The grain size analysis is established for the clay samples around the study area using wet sieving and hydrometer analysis of these samples. Table (4-4) shows the results of the texture analysis of samples around the study area, and classification of Siliciclastic sediments based on Sand, Silt, and Clay content, (After Folk, 1974) in Tucker (1991), (Fig.4.2). According to this classification, all the samples are Sandy mudstone except sample C3 is muddy sandstone (Fig.4.2). The clay percentage of Ahmad Awa area ranges between (43-49) percent in samples (C2-C1) respectively, while the clay percentage in soil samples near Shanaw valley is 19% in sample (C3). In the sample of Helanpe section, the ratio range between (28-36-46) percent in samples (C7-C6-C5) respectively, while the clay percentage in Khurmal area is about 38%, in sample (C8). The highest value of sand portion in Ahmad Awa is 28% while in Shanaw, Helanpe, Banishar and Khurmal area it is (53, 37, and 29) percent respectively. The silt portion represents the intermediate size between the two parts of sand and clay. The highest value of silt in Helanpe is (44%); the lowest value in the same area is 27%. In the other sections (Ahmad Awa, Shanaw, Banishar and Khurmal area), the maximum percentage of silt is (33, 28, 28 and 33) percent respectively.

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Legend

Figure (4.2): Classification of Siliciclastic sediments based on Sand, Silt, and Clay content. (After Folk, 1974) in Tucker (1991), for studied samples of Soil.

Table (4-4): Grain sizes Analysis represent the percentage of Sand, Silt and Clay of the Samples of Studied Area. Sample number

Sand%

Silt%

Clay%

C1

18

33

49

C2

28

29

43

C3

53

28

19

C4

36

28

36

C5

20

34

46

C6

37

27

36

C7

28

44

28

C8

29

33

38

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Summary, Conclusions and Recommendations

CHAPTER FIVE SUMMARY, CONCLUTIONS AND RECOMMENDATIONS 5.1. Summary and Conclusions The following summary and conclusions were drawn from the present study: 1. This study indicates that the Avroman Limestone Formation is entirely composed of pure limestone and no any marl sequence and beds. It has mostly grey colour, hard limestone, fine and coarse grain crystalline limestone, and contains joint and fracture, contain these microfossils (Echinoid. Pelecypode, Foram and some unknown bioclast) and macrofossils such as bivalve Megalodone recorded especially in Banishar valley section. 2. From petrography study, six microfacies have been identified which are: mudstone, wackstone, lithoclastic packstone, oolitic packstone to grainstone, lithoclastic bioclastic grainstone, and peloidal grainstone. The microfossils are relatively rare except Echinoid, Plecypod, Foram and some unknown bioclast. 3. Calcite is a predominant carbonate mineral in limestone of Avroman Formation which is identified through petrographical and mineralogical analysis. The analysis shows that the calcite participates in the total constituent of limestone with a high ratio about 97 % and classified as high pure limestone. 4.

The major clay minerals in the clay samples are (chlorite, illite, montmorillonite) and

the kaolinite appears as a minor clay mineral. Moreover the chlorite appears to be predominant and participates in the total constituents with rate higher than the other clay minerals. 5.

The dominant non-clay mineral in the clay samples is quartz, and calcite is a less

dominant phase after quartz; the plagioclase is another non-clay mineral its percentage is about 17.6 %. 6.

The most abundant (non-carbonate mineral) insoluble residue mineral in the limestone

mainly consists of quartz, clay minerals and iron oxide such as hematite and pyrite, but hematite and pyrite appear as trace minerals.

95

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7. The major Mineral constituents participated in supplying the necessary oxides that are used as cement raw materials are (CaO, SiO₂, Al₂O₃, and Fe₂O₃), the average of chemical composition of limestone of the Avroman Formation is within the standard limits for cement raw materials and appears to be qualified for cement industry. 8.

The relatively high level of CaO and low values of other oxides (SiO₂, MgO, Fe₂O₃,

and Al₂O₃), according to the classification of Kofel (1984), indicated a high degree of purity of the limestone hence its suitability as raw materials for manufacturing Portland cement, and it is classified as high pure limestone. 9.

The chemical modulus of limestone showed that the LSF is very high because of high

purity of limestone. For the present samples the LSF ranges from (178- 478228); this ratio needs to be uniform range for cement making; therefore, clinker compositions and estimating the proportions of raw mix clay and limestone are calculated depending on fixed LSF ( 90 and 95). 10. Although some of the results of the SR and AR are out of the range the standard specification, the clay materials were used to make a mixture and repair both SR and AR. 11. Although there is of clay variability in chemical composition of the clay material, all the components are found to be in agreement with the requirement for manufacturing of Portland cement, when mixed with the limestone of Avroman Formation. 12. Most of the chemical modules of clinker LSF, SR, AR are within the standard specification for manufacturing of Portland cement. Moreover, the cement clinker phases (C₃S, C₂S, C₃A, and C4AF) are mostly within the range according to Brandt (2009). 13.

The cement properties such as hydraulic modules and minimum burnability

temperature are within the standard specification for manufacturing Portland cement. 14. The results of physical properties (water absorption and moisture content) show that the dry process is preferred for manufacturing of Portland cement. 15. The mechanical properties especially compressive strength is within the standard specification for Portland cement according to (Chatterjee, 2004), and easily can be quarried and crushed during manufacturing. 96

Chapter five

Summary, Conclusions and Recommendations

16. Classification Siliciclastic sediment shows that the soil samples of the studied area are sandy mudstone except sample C3 is muddy sandstone,

5.2. Recommendations 1. Purity of limestone of Avroman Formation is very high; therefore, it is recommended to be assessed for using as filler. 2. Due to high purity of limestone and very low iron content, it is recommended that the limestone of this Formation is used for manufacturing white cement because in manufacturing of white cement, the iron content must be minimized to zero. 3. Laboratory study of the clinker properties through selecting a perfect mixing ratio.

97

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Appendices

APPENDICES

Appendix (A) The procedure for staining a thin section of a carbonate rocks has been done according to (Dickson, 1956 in: Adam, 1987) as outlined below: * Prepare two solutions: a. Solution A: Alizarin Reds- concentration of 0.2g/ 100ml of 1.5hydrochloric acid. b. Solution B: Potassium ferricyanid- concentration 2g/100ml of 1.5% hydrochloric acid. 1. Mix solution A and B in the proportion 3 parts by volume of A to 2 parts of B. 2. Sink the thin section in the mixture of solution for 30-45 seconds, agitation gently for at least part of the time to remove gas bubbles from the surface. 3. Wash the stained section in running water for a few seconds. 4. Allow to dry. 5. Cover with polyurethane varnish or a cover slip in the normal way.

Appendix (B) Estimate the amount insoluble residue in the raw materials by prepared 100ml HCl with 10% Concentration according to (Awad and Mashkour, 1980) procedure. Procedure: 1- Grind some amount of the sample to powder using mortar. It is better to use sieve 0.5mm to separate coarse grains, remove the coarse grains, then weight around 3-4gm of the sample. 2- Put the weighed sample in a beaker of 50ml. Add 5ml of diluted HCl (10%) to remove the carbonate from the sample. 3- If there is dolomite in the sample, heat the beaker on sand bath.

1

Appendices 4- If you see still reaction continue, add some HCl to the beaker. 5- Draw the solute on a filter paper and wash the remain of sample using distilled water. 6- Collect and preserve the solution for the other chemical analysis (such as Ca and Mg determination). 7-

Put the sample with filter paper in an oven (less than 100°C) for an hour.

8- Now weigh insoluble residue and find the percentage of it in the sample. I.R. %=( Weight of I.R./Weight of the sample) x100 9- It is possible to draw a log on the columnar stratigraphic section (previous laboratory). 10- Try to give your comments and interpretation for the obtained results.

Appendix (C) Weight and weight percentage of insoluble residue in the samples of limestone (16 gm) of the studied area using the concentration of N10% hydrochloric acid. Sample number A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 Sh1 Sh2 Sh3 Sh4 Sh5 Sh6 Sh7 Sh8 Sh9

Weight insoluble residue by(gm.) 0.232 0.149 0.135 0.430 0.231 0.076 0.197 0.249 0.268 0.427 0.207 0.149 0.427 0.209 0.394 0.264 0.305 0.106 0.162 0.096 0.261 0.042 0.088 0.163 0.168

Weight Insoluble Residue by % 1.450 0.929 0.844 2.688 1.444 0.472 1.231 1.555 1.675 2.669 1.292 0.933 2.669 1.309 2.463 1.650 1.906 0.664 1.011 0.599 1.628 0.260 0.531 1.019 1.051

Sample number Sh10 Sh11 Sh12 Sh13 H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 Bn1 Bn2 Bn3 Bn4 Bn5 Bn6 Bn7 Bn8 Bn9 Bn10

2

Weight insoluble residue by(gm.) 0.255 0.121 0.444 0.032 0.440 0.087 0.590 0.108 0.050 0.097 0.225 0.093 0.131 0.098 0.102 0.238 0.119 0.357 0.080 0.230 0.158 0.280 0.061 0.076 0.076

Weight Insoluble Residue by % 1.594 0.756 2.772 0.201 2.750 0.541 3.688 0.673 0.315 0.603 1.406 0.581 0.819 0.609 0.634 1.489 0.744 2.858 0.500 1.430 0.984 1.751 0.378 2.475 0.475

Appendices

Appendix (D) Chemical composition of mixture and cement clinker with produced some properties. When LSF= 90.

Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

A1+C1 A1+C2 A1+C3 A1+C4 A1+C5 A1+C6 A1+C7 A1+C8 0.342 0.256 0.345 0.224 0.324 0.412 0.48 0.277 0.658 0.744 0.655 0.776 0.676 0.588 0.52 0.723 14.66 15.53 14.03 16.05 14.05 14.03 15.08 14.96 3.94 2.92 4.36 2.41 4.41 4.13 3.87 3.30 2.17 1.62 3.77 1.36 2.82 3.41 2.81 2.21 41.56 42.43 41.18 43.21 40.90 41.07 42.90 41.68 1.24 1.03 1.52 0.78 1.28 1.00 1.35 1.12 0.04 0.04 0.04 0.04 0.05 0.05 0.06 0.05 0.05 0.05 0.07 0.05 0.05 0.06 0.15 0.11 0.36 0.30 0.34 0.22 0.33 0.34 0.37 0.36 36.02 36.07 34.68 35.88 36.12 35.92 33.42 36.21 100.05 100.00 100.00 100.00 100.00 100.00 100.00 100.00 22.90 24.30 21.48 25.03 22.00 21.89 22.64 23.45 6.15 4.57 6.68 3.76 6.90 6.45 5.81 5.17 3.39 2.53 5.77 2.12 4.41 5.32 4.22 3.46 64.91 66.38 63.05 67.39 64.03 64.08 64.43 65.35 1.94 1.61 2.33 1.22 2.00 1.55 2.02 1.76 0.07 0.06 0.06 0.07 0.07 0.08 0.09 0.08 0.09 0.08 0.10 0.08 0.08 0.09 0.22 0.17 0.56 0.48 0.53 0.34 0.52 0.53 0.56 0.56 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 90.05 89.92 90.09 89.91 90.08 90.01 90.20 89.93 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.40 3.42 1.73 4.25 1.95 1.86 2.26 2.72 1.81 1.80 1.16 1.77 1.56 1.21 1.38 1.49 43.86 51.08 40.07 55.66 40.62 43.36 44.89 47.86 32.56 31.12 31.36 29.77 32.43 30.05 31.05 31.13 10.57 7.82 7.95 6.36 10.82 8.08 8.26 7.85 10.33 7.71 17.56 6.46 13.41 16.19 12.84 10.53 2.00 2.11 1.86 2.18 1.92 1.90 1.97 2.04 1359.77 1435.13 1261.28 1476.74 1305.48 1292.88 1339.24 1383.37 2.16 3.38 1.61 4.45 1.72 1.83 2.13 2.60 28.75 21.63 36.05 17.75 33.27 33.57 29.82 25.87 3

Appendices

Continued….D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

A2+C1 A2+C2 A2+C3 A2+C4 A2+C5 A2+C6 A2+C7 A2+C8 0.345 0.258 0.348 0.226 0.327 0.415 0.484 0.279 0.655 0.742 0.652 0.774 0.673 0.585 0.516 0.72 14.75 15.61 14.12 16.15 14.15 14.10 15.17 15.03 3.93 2.89 4.36 2.38 4.40 4.12 3.86 3.27 2.19 1.63 3.79 1.37 2.84 3.43 2.83 2.22 41.74 42.68 41.36 43.47 41.08 41.24 43.04 41.92 1.24 1.02 1.52 0.78 1.28 0.99 1.35 1.12 0.04 0.04 0.04 0.04 0.04 0.05 0.06 0.04 0.05 0.04 0.06 0.04 0.04 0.05 0.15 0.10 0.35 0.29 0.33 0.20 0.32 0.33 0.36 0.34 35.79 35.82 34.44 35.61 35.88 35.71 33.20 35.97 100.07 100.02 100.02 100.02 100.02 100.02 100.02 100.02 22.95 24.32 21.53 25.07 22.06 21.92 22.71 23.47 6.11 4.50 6.64 3.69 6.86 6.40 5.78 5.11 3.40 2.53 5.79 2.12 4.42 5.33 4.23 3.46 64.94 66.48 63.07 67.48 64.05 64.12 64.41 65.45 1.93 1.60 2.32 1.21 1.99 1.54 2.02 1.75 0.06 0.06 0.06 0.06 0.06 0.08 0.08 0.07 0.08 0.07 0.09 0.06 0.07 0.08 0.22 0.16 0.54 0.45 0.51 0.31 0.50 0.52 0.54 0.54 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 89.95 90.06 90.00 89.97 89.96 89.99 89.97 90.12 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.41 3.46 1.73 4.32 1.96 1.87 2.27 2.74 1.80 1.78 1.15 1.74 1.55 1.20 1.37 1.48 43.87 51.78 40.08 56.17 40.55 43.54 44.49 48.65 32.70 30.66 31.48 29.51 32.64 30.01 31.54 30.58 10.44 7.65 7.81 6.18 10.69 7.95 8.16 7.68 10.34 7.70 17.61 6.45 13.45 16.22 12.88 10.53 2.00 2.12 1.86 2.19 1.92 1.91 1.97 2.04 1360.10 1439.03 1261.21 1479.83 1305.16 1293.77 1337.31 1387.58 2.17 3.46 1.61 4.56 1.72 1.84 2.11 2.67 28.582 21.374 35.919 17.480 33.134 33.425 29.736 25.62 4

Appendices

Continued….D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

A3+C1 A3+C2 A3+C3 A3+C4 A3+C5 A3+C6 A3+C7 A3+C8 0.346 0.259 0.35 0.227 0.328 0.417 0.486 0.281 0.654 0.741 0.65 0.773 0.672 0.583 0.514 0.719 14.70 15.57 14.11 16.11 14.10 14.09 15.16 15.04 3.91 2.87 4.35 2.35 4.38 4.11 3.86 3.27 2.20 1.64 3.82 1.38 2.85 3.45 2.85 2.24 41.70 42.62 41.27 43.40 41.03 41.16 42.98 41.82 1.24 1.03 1.53 0.78 1.28 1.00 1.35 1.12 0.03 0.03 0.03 0.03 0.03 0.04 0.05 0.04 0.05 0.04 0.06 0.04 0.04 0.05 0.15 0.10 0.34 0.29 0.33 0.19 0.31 0.33 0.36 0.34 35.82 35.86 34.44 35.64 35.92 35.72 33.21 35.98 100.00 99.94 99.95 99.94 99.95 99.95 99.96 99.94 22.91 24.30 21.54 25.06 22.01 21.93 22.72 23.51 6.10 4.48 6.65 3.66 6.85 6.41 5.78 5.10 3.43 2.56 5.84 2.15 4.45 5.37 4.26 3.50 64.97 66.51 63.01 67.50 64.08 64.08 64.38 65.38 1.94 1.60 2.33 1.21 2.00 1.55 2.03 1.76 0.05 0.04 0.05 0.05 0.05 0.07 0.07 0.06 0.08 0.07 0.09 0.06 0.07 0.08 0.22 0.16 0.53 0.45 0.50 0.30 0.49 0.51 0.54 0.53 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 90.14 90.20 89.85 90.07 90.14 89.89 89.90 89.85 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.41 3.45 1.73 4.31 1.95 1.86 2.26 2.37 1.78 1.75 1.14 1.71 1.54 1.19 1.36 1.78 44.39 52.22 39.68 56.54 41.04 43.30 44.33 43.55 32.20 30.26 31.81 29.19 32.15 30.20 31.69 32.63 10.36 7.55 7.74 6.07 10.61 7.89 8.11 10.47 10.42 7.78 17.76 6.53 13.55 16.34 12.97 10.52 2.00 2.12 1.85 2.19 1.92 1.90 1.97 1.99 1361.72 1440.40 1257.73 1480.95 1306.44 1291.33 1335.66 1354.22 2.19 3.50 1.59 4.60 1.74 1.83 2.10 2.07 28.59 21.36 36.05 17.44 33.17 33.52 29.79 29.06 5

Appendices

Continued…D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

Sh1+C1 Sh1+C2 Sh1+C3 Sh1+C4 Sh1+C5 Sh1+C6 Sh1+C7 Sh1+C8 0.346 0.259 0.349 0.227 0.328 0.417 0.485 0.281 0.654 0.741 0.651 0.773 0.672 0.583 0.525 0.719 14.73 15.60 14.09 16.14 14.12 14.11 15.15 15.07 3.92 2.88 4.35 2.36 4.39 4.12 3.86 3.27 2.19 1.63 3.81 1.37 2.84 3.44 2.83 2.23 41.73 42.66 41.35 43.44 41.06 41.19 43.59 41.85 1.28 1.06 1.56 0.82 1.31 1.02 1.38 1.16 0.04 0.03 0.04 0.04 0.04 0.05 0.05 0.04 0.05 0.04 0.06 0.04 0.04 0.05 0.15 0.10 0.35 0.29 0.33 0.20 0.32 0.33 0.36 0.35 35.85 35.89 34.49 35.67 35.94 35.75 33.68 36.01 100.13 100.09 100.08 100.09 100.08 100.07 101.06 100.08 22.92 24.30 21.49 25.06 22.02 21.93 22.49 23.51 6.10 4.48 6.63 3.67 6.85 6.41 5.72 5.11 3.41 2.54 5.80 2.13 4.43 5.35 4.21 3.48 64.92 66.45 63.05 67.44 64.03 64.03 64.69 65.32 1.98 1.66 2.38 1.27 2.05 1.59 2.05 1.81 0.05 0.05 0.05 0.06 0.06 0.07 0.08 0.06 0.08 0.07 0.09 0.06 0.07 0.08 0.22 0.16 0.54 0.46 0.51 0.31 0.50 0.52 0.54 0.54 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 90.11 90.17 90.16 90.04 90.11 89.87 91.26 89.82 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.41 3.46 1.73 4.32 1.95 1.87 2.26 2.74 1.79 1.76 1.14 1.72 1.54 1.20 1.36 1.47 44.14 51.93 40.33 56.23 40.79 43.08 47.75 47.73 32.40 30.49 31.19 29.43 32.36 30.38 28.46 31.40 10.39 7.59 7.75 6.11 10.64 7.92 8.05 7.64 10.38 7.73 17.66 6.48 13.49 16.29 12.80 10.60 2.00 2.12 1.86 2.19 1.92 1.90 2.00 2.03 1361.10 1439.56 1261.92 1479.99 1305.90 1290.89 1353.44 1382.68 2.18 3.48 1.62 4.58 1.73 1.82 2.29 2.62 28.62 21.40 35.98 17.50 33.19 33.54 29.52 25.74 6

Appendices

Continued…D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

Sh3+C1 Sh3+C2 Sh3+C3 Sh3+C4 Sh3+C5 Sh3+C6 Sh3+C7 Sh3+C8 0.342 0.256 0.345 0.224 0.324 0.412 0.481 0.277 0.658 0.744 0.655 0.776 0.676 0.598 0.519 0.723 14.68 15.55 14.05 16.07 14.07 14.05 15.12 14.98 3.93 2.91 4.36 2.40 4.40 4.13 3.87 3.29 2.19 1.64 3.78 1.38 2.83 3.42 2.83 2.22 41.62 42.50 41.24 43.28 40.96 41.67 42.92 41.75 1.25 1.03 1.53 0.79 1.28 1.01 1.35 1.13 0.03 0.03 0.03 0.03 0.03 0.04 0.05 0.04 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 0.36 0.31 0.35 0.22 0.34 0.35 0.38 0.36 35.77 35.79 34.43 35.58 35.87 36.13 33.20 35.93 99.88 99.81 99.83 99.80 99.82 100.84 99.87 99.81 22.90 24.30 21.49 25.03 22.00 21.71 22.68 23.46 6.14 4.55 6.66 3.74 6.88 6.38 5.81 5.15 3.41 2.55 5.78 2.15 4.42 5.29 4.24 3.48 64.92 66.39 63.06 67.40 64.04 64.39 64.38 65.36 1.95 1.62 2.34 1.23 2.01 1.55 2.03 1.77 0.05 0.04 0.05 0.05 0.05 0.07 0.07 0.06 0.08 0.06 0.09 0.06 0.07 0.08 0.22 0.16 0.57 0.49 0.53 0.35 0.53 0.54 0.57 0.57 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 90.08 89.95 90.12 89.95 90.11 91.22 89.98 89.97 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.40 3.42 1.73 4.25 1.95 1.86 2.26 2.72 1.80 1.78 1.15 1.74 1.55 1.21 1.37 1.48 44.03 51.27 40.25 55.85 40.81 46.58 44.41 48.06 32.43 30.98 31.24 29.62 32.30 27.09 31.53 30.99 10.49 7.74 7.88 6.28 10.74 7.95 8.22 7.77 10.38 7.77 17.60 6.53 13.46 16.08 12.90 10.59 2.00 2.11 1.86 2.18 1.92 1.93 1.97 2.04 1360.22 1435.55 1261.85 1477.11 1306.02 1309.17 1336.49 1383.85 2.17 3.39 1.62 4.48 1.73 1.98 2.10 2.62 28.72 21.61 36.01 17.74 33.24 33.26 29.85 25.84 7

Appendices

Continued…D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

Sh4C1 Sh4+C2 Sh4+C3 Sh4+C4 Sh4+C5 Sh4+C6 Sh4+C7 Sh4+C8 0.345 0.259 0.348 0.226 0.327 0.415 0.484 0.28 0.655 0.741 0.652 0.774 0.673 0.585 0.516 0.72 14.65 15.56 14.02 16.03 14.05 14.01 15.10 14.98 3.90 2.87 4.33 2.34 4.37 4.10 3.84 3.25 2.19 1.63 3.79 1.37 2.84 3.43 2.83 2.22 41.59 42.45 41.21 43.28 40.92 41.10 42.91 41.70 1.18 0.95 1.46 0.70 1.21 0.93 1.30 1.05 0.02 0.02 0.02 0.02 0.03 0.04 0.04 0.03 0.05 0.04 0.06 0.04 0.04 0.05 0.15 0.10 0.34 0.29 0.33 0.19 0.31 0.33 0.36 0.34 35.81 35.81 34.46 35.76 35.90 35.73 33.22 35.96 99.72 99.63 99.67 99.74 99.66 99.71 99.74 99.64 22.93 24.39 21.50 25.06 22.03 21.90 22.69 23.52 6.10 4.50 6.64 3.66 6.86 6.40 5.78 5.11 3.42 2.56 5.82 2.14 4.45 5.36 4.25 3.49 65.07 66.52 63.18 67.64 64.17 64.23 64.51 65.49 1.84 1.49 2.24 1.09 1.90 1.46 1.95 1.65 0.04 0.03 0.04 0.03 0.04 0.06 0.07 0.04 0.08 0.07 0.09 0.06 0.07 0.08 0.22 0.16 0.53 0.45 0.50 0.30 0.49 0.51 0.54 0.53 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 90.10 89.78 90.15 90.14 90.11 90.13 90.08 89.86 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.41 3.46 1.73 4.32 1.95 1.86 2.26 2.73 1.79 1.76 1.14 1.72 1.54 1.19 1.36 1.46 44.63 51.49 40.80 57.15 41.31 44.22 45.06 48.40 32.06 31.07 30.86 28.74 31.99 29.43 31.06 30.92 10.39 7.60 7.75 6.10 10.64 7.90 8.11 7.63 10.40 7.78 17.70 6.50 13.53 16.30 12.94 10.63 2.01 2.12 1.86 2.19 1.93 1.91 1.97 2.04 1362.94 1436.97 1263.43 1484.00 1307.76 1295.96 1339.37 1385.37 2.20 3.44 1.64 4.66 1.75 1.87 2.14 2.65 28.49 21.29 35.87 17.29 33.07 33.37 29.67 25.58 8

Appendices

Continued….D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

H1+C1 H1+C2 H1+C3 H1+C4 H1+C5 H1+C6 H1+C7 H1+C8 0.312 0.231 0.315 0.201 0.294 0.379 0.447 0.25 0.688 0.769 0.685 0.799 0.706 0.621 0.553 0.75 14.73 15.03 13.71 15.45 13.68 13.72 14.77 14.49 4.21 3.20 4.48 2.74 4.51 4.25 4.01 3.52 2.89 2.41 4.28 2.21 3.43 3.90 3.30 2.92 40.77 41.93 40.84 42.62 40.62 40.78 42.48 41.29 1.17 0.94 1.40 0.71 1.17 0.92 1.26 1.02 0.02 0.01 0.02 0.01 0.02 0.03 0.04 0.02 0.05 0.04 0.05 0.04 0.04 0.05 0.13 0.09 0.33 0.26 0.30 0.18 0.29 0.31 0.34 0.31 35.55 35.80 34.56 35.62 35.89 35.72 33.39 35.94 99.70 99.61 99.65 99.59 99.64 99.68 99.72 99.62 22.96 23.55 21.07 24.16 21.46 21.45 22.27 22.76 6.56 5.01 6.89 4.29 7.08 6.65 6.04 5.54 4.50 3.78 6.58 3.45 5.37 6.10 4.97 4.58 63.56 65.71 62.74 66.63 63.71 63.76 64.06 64.85 1.82 1.47 2.15 1.11 1.83 1.44 1.90 1.61 0.03 0.02 0.03 0.02 0.03 0.05 0.06 0.03 0.07 0.06 0.08 0.06 0.06 0.08 0.20 0.15 0.51 0.41 0.46 0.28 0.45 0.48 0.51 0.49 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 89.96 89.79 89.95 89.92 90.30 90.04 89.92 90.06 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.06 2.68 1.56 3.12 1.72 1.68 2.02 2.25 1.45 1.33 1.05 1.24 1.32 1.09 1.21 1.21 43.09 49.41 39.53 53.83 40.93 43.00 43.71 47.22 31.55 30.25 30.59 28.64 30.65 29.07 30.86 29.63 9.49 6.88 7.12 5.53 9.67 7.30 7.59 6.92 13.48 11.49 20.03 10.50 16.35 18.56 15.13 13.94 1.94 2.03 1.82 2.09 1.88 1.86 1.92 1.97 1318.51 1383.48 1230.71 1420.81 1274.13 1264.25 1307.46 1340.87 1.88 2.76 1.49 3.44 1.61 1.70 1.92 2.26 31.56 25.48 38.20 22.11 35.70 35.71 31.97 29.18

9

Appendices

Continued…D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

H2+C1 H2+C2 H2+C3 H2+C4 H2+C5 H2+C6 H2+C7 H2+C8 0.347 0.26 0.35 0.227 0.329 0.417 0.486 0.281 0.653 0.74 0.65 0.773 0.671 0.593 0.514 0.719 14.73 15.61 14.09 16.09 14.12 14.07 15.15 15.02 3.90 2.86 4.33 2.33 4.38 4.10 3.84 3.24 2.19 1.63 3.81 1.36 2.85 3.44 2.83 2.23 41.71 42.64 41.33 43.47 41.05 41.77 43.02 41.88 1.15 0.92 1.44 0.67 1.19 0.92 1.28 1.02 0.02 0.02 0.02 0.02 0.03 0.04 0.04 0.03 0.05 0.04 0.06 0.04 0.04 0.05 0.15 0.10 0.34 0.29 0.33 0.19 0.31 0.33 0.36 0.34 36.15 36.22 34.79 36.05 36.25 36.47 33.48 36.36 100.25 100.23 100.20 100.24 100.21 101.18 100.16 100.22 22.97 24.38 21.54 25.07 22.07 21.74 22.72 23.51 6.09 4.47 6.63 3.63 6.84 6.33 5.76 5.08 3.42 2.55 5.82 2.13 4.45 5.31 4.25 3.48 65.07 66.61 63.18 67.73 64.17 64.55 64.52 65.58 1.80 1.44 2.20 1.04 1.86 1.42 1.92 1.60 0.04 0.03 0.04 0.04 0.04 0.06 0.07 0.05 0.08 0.07 0.09 0.06 0.07 0.08 0.22 0.16 0.53 0.45 0.50 0.30 0.49 0.51 0.54 0.53 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 89.94 89.91 89.99 90.23 89.92 91.23 90.01 90.01 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.42 3.48 1.73 4.35 1.95 1.87 2.27 2.75 1.78 1.75 1.14 1.71 1.54 1.19 1.36 1.46 44.41 52.10 40.58 57.67 41.02 47.27 45.03 49.05 32.36 30.60 31.13 28.36 32.34 26.67 31.16 30.41 10.36 7.53 7.71 6.03 10.61 7.79 8.08 7.56 10.40 7.75 17.72 6.47 13.54 16.17 12.94 10.60 2.00 2.12 1.86 2.20 1.92 1.93 1.97 2.04 1362.10 1440.32 1262.38 1486.95 1306.49 1311.79 1339.35 1388.88 2.20 3.50 1.63 4.74 1.74 2.02 2.14 2.70 28.41 21.13 35.81 17.13 33.00 33.02 29.60 25.42 10

Appendices

Continued….D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

H3+C1 H3+C2 H3+C3 H3+C4 H3+C5 H3+C6 H3+C7 H3+C8 0.322 0.239 0.325 0.208 0.304 0.388 0.458 0.259 0.678 0.761 0.675 0.792 0.696 0.612 0.542 0.741 14.38 15.15 13.79 15.57 13.78 13.73 14.84 14.62 4.16 3.23 4.56 2.76 4.60 4.30 4.05 3.58 2.61 2.15 4.11 1.92 3.22 3.72 3.13 2.68 41.21 42.00 40.86 42.73 40.61 40.86 42.55 41.31 1.34 1.15 1.60 0.93 1.37 1.09 1.42 1.24 0.04 0.04 0.04 0.04 0.05 0.05 0.06 0.05 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 0.33 0.28 0.32 0.19 0.30 0.32 0.35 0.33 35.63 35.63 34.37 35.45 35.72 35.61 33.22 35.77 99.75 99.66 99.70 99.65 99.69 99.73 99.76 99.67 22.42 23.65 21.11 24.26 21.54 21.42 22.31 22.88 6.49 5.05 6.98 4.30 7.18 6.70 6.09 5.60 4.07 3.35 6.29 3.00 5.04 5.80 4.71 4.20 64.28 65.59 62.53 66.56 63.49 63.72 63.94 64.66 2.09 1.80 2.45 1.45 2.15 1.71 2.14 1.94 0.07 0.06 0.06 0.07 0.07 0.08 0.09 0.08 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.15 0.52 0.44 0.49 0.30 0.48 0.50 0.53 0.51 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 89.94 89.90 89.95 90.15 90.17 90.56 90.00 89.95 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.12 2.82 1.59 3.32 1.76 1.71 2.07 2.34 1.59 1.51 1.11 1.44 1.43 1.16 1.29 1.33 41.68 48.37 38.08 53.22 39.11 43.11 42.89 45.54 32.85 31.32 31.79 29.40 32.24 28.88 31.60 31.23 10.30 7.70 7.84 6.34 10.52 7.94 8.17 7.73 12.39 10.20 19.15 9.12 15.32 17.65 14.32 12.77 1.95 2.05 1.82 2.11 1.88 1.88 1.93 1.98 1325.01 1392.14 1232.69 1432.49 1275.76 1273.84 1311.87 1345.09 1.88 2.77 1.44 3.53 1.55 1.72 1.91 2.22 31.36 25.04 38.18 21.53 35.64 35.51 31.81 28.90 11

Appendices

Continued…D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

Bn1+C1 Bn1+C2 Bn1+C3 Bn1+C4 Bn1+C5 Bn1+C6 Bn1+C7 Bn1+C8 0.341 0.255 0.344 0.223 0.323 0.411 0.48 0.276 0.659 0.745 0.656 0.777 0.677 0.589 0.52 0.724 14.54 15.39 13.92 15.89 13.94 13.93 15.02 14.83 3.94 2.93 4.37 2.42 4.41 4.13 3.88 3.30 2.24 1.70 3.83 1.44 2.88 3.46 2.87 2.28 41.21 42.04 40.83 42.81 40.55 40.75 42.59 41.31 1.34 1.14 1.62 0.91 1.38 1.09 1.43 1.24 0.03 0.03 0.03 0.03 0.03 0.04 0.05 0.04 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 0.34 0.29 0.33 0.20 0.32 0.33 0.36 0.34 36.02 36.07 34.68 35.88 36.12 35.91 33.40 36.21 99.72 99.63 99.67 99.61 99.66 99.71 99.74 99.64 22.83 24.21 21.42 24.94 21.93 21.84 22.64 23.38 6.19 4.60 6.72 3.79 6.93 6.48 5.85 5.21 3.52 2.67 5.89 2.26 4.54 5.43 4.32 3.59 64.69 66.15 62.83 67.17 63.81 63.88 64.20 65.12 2.11 1.80 2.50 1.42 2.18 1.71 2.16 1.95 0.05 0.04 0.05 0.05 0.05 0.07 0.07 0.06 0.08 0.06 0.09 0.06 0.07 0.08 0.22 0.16 0.54 0.45 0.51 0.31 0.50 0.52 0.54 0.54 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 90.00 89.94 90.04 89.97 90.04 89.94 89.90 89.93 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.35 3.33 1.70 4.12 1.91 1.83 2.23 2.66 1.76 1.72 1.14 1.68 1.53 1.19 1.35 1.45 43.10 50.42 39.32 55.10 39.87 42.63 43.64 47.17 32.94 31.38 31.74 29.92 32.80 30.45 31.98 31.44 10.45 7.68 7.83 6.22 10.70 7.98 8.18 7.71 10.70 8.12 17.93 6.88 13.80 16.53 13.15 10.94 1.99 2.10 1.85 2.17 1.91 1.89 1.96 2.02 1336.63 1409.42 1239.47 1449.69 1283.29 1270.30 1314.25 1358.64 2.09 3.28 1.56 4.32 1.67 1.78 2.05 2.53 29.25 22.17 36.55 18.30 33.80 34.03 30.26 26.41 12

Appendices

Continued…D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

Bn2+C1 Bn2+C2 Bn2+C3 Bn2+C4 Bn2+C5 Bn2+C6 Bn2+C7 Bn2+C8 0.341 0.255 0.344 0.223 0.323 0.411 0.479 0.276 0.659 0.745 0.656 0.777 0.677 0.589 0.521 0.724 14.58 15.43 13.96 15.94 13.98 13.97 15.02 14.87 3.98 2.97 4.40 2.46 4.45 4.17 3.90 3.35 2.19 1.64 3.78 1.38 2.83 3.42 2.82 2.22 41.44 42.30 41.06 43.08 40.78 40.96 42.80 41.56 1.16 0.94 1.44 0.69 1.19 0.92 1.28 1.03 0.06 0.06 0.06 0.06 0.06 0.07 0.07 0.06 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 0.36 0.30 0.34 0.21 0.33 0.34 0.37 0.35 36.07 36.13 34.74 35.94 36.17 35.96 33.46 36.27 99.88 99.81 99.84 99.81 99.83 99.85 99.87 99.82 22.85 24.24 21.44 24.96 21.96 21.86 22.62 23.40 6.24 4.66 6.77 3.85 6.99 6.52 5.88 5.26 3.43 2.57 5.80 2.16 4.44 5.35 4.25 3.50 64.94 66.43 63.08 67.46 64.07 64.10 64.45 65.39 1.82 1.47 2.21 1.08 1.87 1.45 1.93 1.63 0.09 0.09 0.09 0.10 0.09 0.10 0.11 0.10 0.08 0.06 0.09 0.06 0.07 0.08 0.22 0.16 0.56 0.48 0.53 0.34 0.52 0.53 0.56 0.56 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 89.96 89.89 90.00 89.93 90.00 89.91 90.10 89.88 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.36 3.35 1.71 4.15 1.92 1.84 2.23 2.67 1.82 1.81 1.17 1.78 1.57 1.22 1.38 1.51 43.61 50.99 39.83 55.68 40.40 43.08 44.64 47.72 32.62 31.02 31.43 29.55 32.47 30.16 31.16 31.09 10.74 8.01 8.11 6.56 11.00 8.24 8.39 8.03 10.43 7.82 17.66 6.57 13.52 16.28 12.92 10.64 2.00 2.11 1.85 2.18 1.92 1.90 1.97 2.03 1341.11 1414.35 1244.00 1454.73 1287.99 1274.40 1320.55 1363.52 2.12 3.31 1.58 4.35 1.69 1.80 2.09 2.56 28.97 21.87 36.27 18.00 33.50 33.77 30.00 26.11 13

Appendices

Continued…D Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

Bn3+C1 Bn3+C2 Bn3+C3 Bn3+C4 Bn3+C5 Bn3+C6 Bn3+C7 Bn3+C8 0.336 0.251 0.339 0.219 0.319 0.406 0.474 0.272 0.664 0.749 0.661 0.781 0.681 0.594 0.526 0.728 14.56 15.40 13.94 15.87 14.00 13.96 15.01 14.86 4.00 3.01 4.42 2.51 4.47 4.19 3.92 3.38 2.35 1.83 3.91 1.58 2.99 3.55 2.94 2.40 41.55 42.41 41.18 43.19 40.87 41.05 42.86 41.66 1.17 0.95 1.44 0.71 1.20 0.93 1.29 1.05 0.04 0.04 0.04 0.05 0.05 0.05 0.06 0.05 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 0.37 0.32 0.36 0.23 0.35 0.36 0.38 0.37 35.58 35.57 34.26 35.37 35.65 35.51 33.09 35.71 99.67 99.57 99.62 99.55 99.61 99.66 99.70 99.59 22.71 24.07 21.33 24.73 21.88 21.77 22.54 23.27 6.24 4.70 6.76 3.91 6.99 6.52 5.89 5.29 3.66 2.86 5.99 2.46 4.68 5.53 4.42 3.76 64.84 66.26 63.01 67.30 63.90 64.00 64.34 65.22 1.82 1.48 2.21 1.10 1.88 1.46 1.93 1.64 0.07 0.07 0.07 0.07 0.07 0.08 0.09 0.08 0.07 0.06 0.09 0.06 0.07 0.08 0.21 0.16 0.58 0.50 0.55 0.37 0.54 0.55 0.58 0.58 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 90.11 89.96 90.14 90.18 89.84 89.93 90.08 89.87 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 2.29 3.18 1.67 3.88 1.88 1.81 2.19 2.57 1.70 1.65 1.13 1.59 1.49 1.18 1.33 1.41 43.96 50.97 40.22 56.03 40.00 43.11 44.55 47.54 31.96 30.55 30.82 28.64 32.56 29.88 31.00 30.85 10.34 7.62 7.77 6.18 10.61 7.93 8.13 7.66 11.15 8.69 18.23 7.50 14.23 16.84 13.45 11.44 1.99 2.10 1.85 2.16 1.90 1.89 1.96 2.02 1334.94 1404.66 1239.69 1445.87 1278.80 1268.62 1314.49 1354.00 2.10 3.21 1.58 4.20 1.65 1.78 2.06 2.49 29.51 22.65 36.66 18.87 34.04 34.20 30.42 26.79

14

Appendices

Appendix (E) Chemical composition of mixture and cement clinker with produced some properties. When LSF = 95.

Requirments A1+C1 A1+C2 A1+C3 A1+C4 A1+C5 A1+C6 A1+C7 A1+C8 X= 0.328 0.245 0.331 0.214 0.311 0.395 0.46 0.265 Y= 0.672 0.755 0.669 0.786 0.689 0.605 0.54 0.735 SiO₂ 14.07 14.90 13.51 15.34 13.45 13.49 14.46 14.32 Al₂O₃ 3.79 2.81 4.21 2.31 4.22 3.98 3.71 3.16 Fe₂O₃ 2.08 1.55 3.63 1.30 2.70 3.28 2.69 2.11 Raw mix CaO 42.12 42.96 41.71 43.72 41.43 41.62 43.42 42.28 MgO 1.21 1.01 1.48 0.77 1.24 0.98 1.31 1.10 SO₃ 0.04 0.04 0.04 0.04 0.05 0.05 0.06 0.05 Na₂O 0.05 0.05 0.06 0.05 0.05 0.06 0.14 0.11 K2O 0.34 0.29 0.33 0.21 0.32 0.33 0.36 0.34 L.O.I 36.34 36.38 35.01 36.20 36.37 36.22 33.85 36.53 ToTal 100.04 99.99 99.98 99.94 99.82 100.00 100.00 100.00 SiO₂ 22.08 23.42 20.80 24.07 21.21 21.15 21.85 22.57 Al₂O₃ 5.94 4.41 6.47 3.62 6.65 6.23 5.61 4.98 Fe₂O₃ 3.27 2.44 5.58 2.04 4.25 5.14 4.07 3.33 Clinker CaO 66.12 67.54 64.19 68.59 65.29 65.26 65.63 66.61 MgO 1.90 1.58 2.28 1.21 1.96 1.53 1.98 1.73 SO₃ 0.07 0.06 0.06 0.07 0.07 0.08 0.09 0.08 Na₂O 0.08 0.07 0.10 0.07 0.07 0.09 0.22 0.17 K2O 0.54 0.46 0.51 0.32 0.50 0.52 0.54 0.54 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 95.02 94.85 94.66 95.12 95.21 94.79 95.11 95.20 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.40 3.42 1.72 4.25 1.95 1.86 2.26 2.71 AR 1.82 1.81 1.16 1.77 1.57 1.21 1.38 1.50 C₃S% 56.57 63.66 51.63 68.88 53.66 55.43 57.32 61.22 clinker C₂S% 20.63 19.12 20.67 17.04 20.31 18.83 19.41 18.51 phases C₃A% 10.21 7.56 7.71 6.14 10.45 7.83 7.99 7.57 C₄AF% 9.96 7.43 16.99 6.22 12.93 15.63 12.39 10.13 H.M. 2.11 2.23 1.95 2.31 2.03 2.01 2.08 2.16 clinker M.B.T 1423.07 1496.36 1321.42 1540.29 1371.78 1355.16 1402.02 1449.71 properties B.I 2.88 4.36 2.14 5.72 2.36 2.42 2.81 3.46 L.Ph. 27.77 20.91 34.93 17.14 32.12 32.48 28.83 24.95

15

Appendices

Continued….E Requirments A2+C1 A2+C2 A2+C3 A2+C4 A2+C5 A2+C6 A2+C7 A2+C8 X= 0.331 0.247 0.334 0.216 0.314 0.398 0.463 0.268 Y= 0.669 0.753 0.666 0.784 0.686 0.602 0.537 0.732 SiO₂ 14.12 14.95 13.56 15.49 13.59 13.60 14.52 14.45 Al₂O₃ 3.76 2.77 4.18 2.28 4.23 3.97 3.70 3.15 Fe₂O₃ 2.09 1.56 3.64 1.31 2.72 3.30 2.71 2.13 Raw mix CaO 42.28 43.20 41.90 43.98 41.65 41.76 43.59 42.47 MgO 1.21 1.00 1.48 0.77 1.24 0.97 1.31 1.09 SO₃ 0.04 0.04 0.04 0.04 0.04 0.05 0.05 0.04 Na₂O 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 K2O 0.33 0.28 0.32 0.19 0.31 0.32 0.35 0.33 L.O.I 36.06 36.11 34.76 35.93 36.16 35.99 33.64 36.26 ToTal 99.93 99.95 99.93 100.02 99.98 100.02 100.02 100.02 SiO₂ 22.10 23.43 20.80 24.17 21.30 21.23 21.88 22.66 Al₂O₃ 5.89 4.34 6.42 3.56 6.62 6.20 5.57 4.93 Fe₂O₃ 3.27 2.44 5.59 2.04 4.27 5.16 4.08 3.34 Clinker CaO 66.20 67.67 64.28 68.61 65.25 65.22 65.68 66.61 MgO 1.89 1.57 2.27 1.19 1.95 1.52 1.98 1.72 SO₃ 0.06 0.06 0.06 0.06 0.06 0.08 0.08 0.07 Na₂O 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.16 K2O 0.52 0.44 0.49 0.30 0.48 0.50 0.53 0.52 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 95.12 95.11 94.83 94.87 94.83 94.47 95.12 94.93 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.41 3.46 1.73 4.31 1.96 1.87 2.27 2.74 AR 1.80 1.78 1.15 1.74 1.55 1.20 1.37 1.48 C₃S% 57.10 64.65 52.32 68.65 53.02 54.88 57.58 60.89 clinker C₂S% 20.29 18.39 20.17 17.50 21.06 19.48 19.29 19.02 phases C₃A% 10.06 7.38 7.55 5.97 10.33 7.71 7.87 7.42 C₄AF% 9.96 7.42 17.01 6.22 12.98 15.70 12.41 10.16 H.M. 2.12 2.24 1.96 2.30 2.03 2.00 2.08 2.15 clinker M.B.T 1425.94 1501.64 1324.89 1539.82 1368.58 1352.26 1403.43 1448.37 properties B.I 2.93 4.49 2.18 5.78 2.33 2.40 2.84 3.46 L.Ph. 27.57 20.63 34.74 16.89 32.03 32.40 28.69 24.77 16

Appendices

Continued…E Requirments A3+C1 A3+C2 A3+C3 A3+C4 A3+C5 A3+C6 A3+C7 A3+C8 X= 0.332 0.249 0.335 0.218 0.315 0.400 0.465 0.269 Y= 0.668 0.751 0.665 0.782 0.685 0.600 0.535 0.731 SiO₂ 14.11 14.97 13.55 15.40 13.58 13.51 14.51 14.40 Al₂O₃ 3.76 2.76 4.18 2.25 4.23 3.95 3.69 3.13 Fe₂O₃ 2.11 1.58 3.67 1.32 2.75 3.31 2.72 2.14 Raw mix CaO 42.27 43.13 41.83 43.90 41.63 41.76 43.53 42.42 MgO 1.21 1.01 1.49 0.77 1.25 0.97 1.31 1.10 SO₃ 0.03 0.03 0.03 0.03 0.03 0.04 0.05 0.04 Na₂O 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 K2O 0.33 0.27 0.31 0.19 0.30 0.32 0.34 0.32 L.O.I 36.13 36.15 34.78 35.95 36.23 36.04 33.65 36.30 ToTal 99.99 99.93 99.90 99.85 100.05 99.95 99.96 99.94 SiO₂ 22.09 23.47 20.80 24.11 21.28 21.14 21.88 22.62 Al₂O₃ 5.88 4.33 6.42 3.53 6.62 6.18 5.57 4.91 Fe₂O₃ 3.30 2.47 5.64 2.07 4.30 5.18 4.11 3.37 Clinker CaO 66.19 67.61 64.24 68.70 65.24 65.34 65.65 66.65 MgO 1.90 1.58 2.28 1.20 1.96 1.53 1.98 1.72 SO₃ 0.05 0.04 0.05 0.05 0.05 0.07 0.07 0.06 Na₂O 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.16 K2O 0.51 0.43 0.48 0.29 0.47 0.49 0.52 0.51 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 95.14 94.87 94.74 95.25 94.84 95.00 95.07 95.12 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.41 3.45 1.73 4.31 1.95 1.86 2.26 2.73 AR 1.78 1.75 1.14 1.71 1.54 1.19 1.36 1.46 C₃S% 57.17 64.14 52.08 69.70 53.03 56.21 57.47 61.41 clinker C₂S% 20.21 18.90 20.35 16.53 21.01 18.21 19.38 18.53 phases C₃A% 10.00 7.30 7.48 5.85 10.27 7.61 7.81 7.32 C₄AF% 10.05 7.52 17.15 6.29 13.10 15.76 12.50 10.26 H.M. 2.12 2.23 1.95 2.31 2.03 2.01 2.08 2.16 clinker M.B.T 1425.31 1498.35 1322.21 1544.20 1367.40 1357.89 1402.02 1449.93 properties B.I 2.93 4.44 2.16 5.90 2.33 2.46 2.83 3.49 L.Ph. 27.61 20.67 34.85 16.82 32.10 32.35 28.74 24.77 17

Appendices

Continued…E Requirments X= Y= SiO₂ Al₂O₃ Fe₂O₃ Raw mix CaO MgO SO₃ Na₂O K2O L.O.I ToTal SiO₂ Al₂O₃ Fe₂O₃ Clinker CaO MgO SO₃ Na₂O K2O L.O.I ToTal LSF* LSF** Ratio SR AR C₃S% clinker C₂S% phases C₃A% C₄AF% H.M. clinker M.B.T properties B.I L.Ph.

Sh1+C1 Sh1+C2 Sh1+C3 Sh1+C4 Sh1+C5 Sh1+C6 Sh1+C7 Sh1+C8 0.332 0.249 0.335 0.218 0.315 0.400 0.465 0.269 0.668 0.751 0.665 0.782 0.685 0.600 0.535 0.731 14.14 15.00 13.53 15.51 13.57 13.54 14.53 14.43 3.76 2.77 4.18 2.27 4.22 3.95 3.70 3.13 2.10 1.57 3.65 1.32 2.73 3.30 2.72 2.14 42.30 43.17 41.87 43.94 41.65 41.79 43.56 42.45 1.25 1.04 1.52 0.81 1.28 1.00 1.34 1.13 0.04 0.03 0.04 0.04 0.04 0.05 0.05 0.04 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 0.33 0.28 0.32 0.19 0.31 0.32 0.35 0.33 36.16 36.18 34.81 35.98 36.24 36.06 33.67 36.33 100.13 100.09 99.98 100.09 100.08 100.07 100.06 100.09 22.10 23.47 20.76 24.19 21.25 21.15 21.89 22.63 5.88 4.33 6.41 3.54 6.61 6.18 5.57 4.92 3.29 2.46 5.61 2.06 4.28 5.16 4.09 3.35 66.13 67.55 64.26 68.53 65.25 65.29 65.61 66.58 1.95 1.63 2.33 1.26 2.01 1.57 2.02 1.78 0.06 0.05 0.05 0.06 0.06 0.07 0.08 0.06 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.16 0.52 0.44 0.49 0.30 0.48 0.50 0.53 0.52 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 95.10 94.84 95.00 94.77 94.77 94.97 95.04 95.08 95.00 95.00 95.00 95.00 95.00 95.00 0.00 0.00 2.41 3.46 1.73 4.32 1.95 1.86 2.26 2.74 1.79 1.77 1.14 1.72 1.54 1.20 1.36 1.47 56.89 63.84 52.56 68.27 53.42 55.96 57.26 61.10 20.44 19.13 19.88 17.84 20.62 18.41 19.55 18.78 10.02 7.33 7.50 5.91 10.28 7.64 7.84 7.36 10.01 7.47 17.06 6.26 13.02 15.71 12.46 10.20 2.11 2.23 1.96 2.30 2.03 2.01 2.08 2.16 1424.58 1497.50 1325.52 1537.89 1370.14 1357.33 1401.48 1449.08 2.92 4.43 2.19 5.76 2.35 2.45 2.82 3.48 27.64 20.72 34.80 16.93 32.07 32.37 28.76 24.81 18

Appendices

Continued…E Requirments Sh3+C1 Sh3+C2 Sh3+C3 Sh3+C4 Sh3+C5 Sh3+C6 Sh3+C7 Sh3+C8 X= 0.328 0.245 0.331 0.214 0.311 0.395 0.460 0.265 Y= 0.672 0.755 0.669 0.786 0.689 0.605 0.540 0.735 SiO₂ 14.09 14.90 13.49 15.36 13.52 13.48 14.47 14.34 Al₂O₃ 3.78 2.79 4.19 2.30 4.23 3.96 3.71 3.16 Fe₂O₃ 2.10 1.57 3.63 1.32 2.72 3.28 2.70 2.13 Raw mix CaO 42.18 43.06 41.82 43.83 41.54 41.71 43.47 42.34 MgO 1.22 1.01 1.49 0.78 1.25 0.98 1.32 1.10 SO₃ 0.03 0.03 0.03 0.03 0.03 0.04 0.05 0.04 Na₂O 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 K2O 0.35 0.30 0.34 0.21 0.32 0.34 0.36 0.35 L.O.I 36.08 36.11 34.79 35.93 36.16 36.00 33.64 36.25 ToTal 99.87 99.80 99.83 99.80 99.82 99.84 99.86 99.81 SiO₂ 22.08 23.39 20.75 24.06 21.24 21.11 21.86 22.57 Al₂O₃ 5.92 4.39 6.44 3.60 6.64 6.20 5.60 4.96 Fe₂O₃ 3.29 2.46 5.58 2.06 4.27 5.14 4.08 3.35 Clinker CaO 66.13 67.60 64.30 68.62 65.26 65.34 65.64 66.62 MgO 1.91 1.59 2.28 1.22 1.97 1.54 1.99 1.73 SO₃ 0.05 0.04 0.05 0.05 0.05 0.07 0.07 0.06 Na₂O 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.16 K2O 0.55 0.47 0.52 0.34 0.51 0.53 0.55 0.55 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 95.05 95.09 95.06 95.22 95.06 95.13 95.13 95.23 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.40 3.42 1.73 4.25 1.95 1.86 2.26 2.72 AR 1.80 1.78 1.15 1.75 1.56 1.21 1.37 1.48 C₃S% 56.74 64.35 52.74 69.22 53.41 56.34 57.45 61.40 clinker C₂S% 20.51 18.50 19.69 16.75 20.59 18.03 19.32 18.39 phases C₃A% 10.13 7.46 7.62 6.06 10.38 7.74 7.93 7.49 C₄AF% 10.01 7.48 16.98 6.28 12.99 15.64 12.43 10.19 H.M. 2.11 2.24 1.96 2.31 2.03 2.01 2.08 2.16 clinker M.B.T 1423.46 1499.16 1326.81 1541.37 1370.06 1359.50 1402.34 1450.11 properties B.I 2.89 4.42 2.19 5.76 2.34 2.47 2.82 3.47 L.Ph. 27.75 20.86 34.81 17.11 32.12 32.38 28.81 24.92 19

Appendices

Continued…E Requirments Sh4C1 Sh4+C2 Sh4+C3 Sh4+C4 Sh4+C5 Sh4+C6 Sh4+C7 Sh4+C8 X= 0.331 0.248 0.334 0.217 0.314 0.399 0.464 0.268 Y= 0.669 0.752 0.666 0.783 0.686 0.601 0.536 0.732 SiO₂ 14.06 14.90 13.46 15.40 13.49 13.47 14.47 14.34 Al₂O₃ 3.74 2.75 4.16 2.25 4.20 3.94 3.69 3.12 Fe₂O₃ 2.10 1.56 3.64 1.31 2.72 3.30 2.71 2.13 Raw mix CaO 42.16 43.01 41.79 43.77 41.51 41.66 43.44 42.30 MgO 1.14 0.93 1.41 0.69 1.18 0.91 1.26 1.02 SO₃ 0.02 0.02 0.02 0.02 0.03 0.04 0.04 0.03 Na₂O 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 K2O 0.33 0.27 0.31 0.19 0.30 0.31 0.34 0.32 L.O.I 36.11 36.14 34.82 35.94 36.20 36.02 33.64 36.28 ToTal 99.71 99.62 99.67 99.61 99.66 99.70 99.73 99.63 SiO₂ 22.11 23.47 20.75 24.18 21.26 21.16 21.90 22.63 Al₂O₃ 5.89 4.33 6.41 3.54 6.62 6.19 5.58 4.92 Fe₂O₃ 3.30 2.46 5.62 2.06 4.29 5.18 4.10 3.36 Clinker CaO 66.29 67.75 64.43 68.75 65.40 65.42 65.72 66.77 MgO 1.80 1.46 2.18 1.08 1.85 1.43 1.91 1.61 SO₃ 0.04 0.03 0.04 0.03 0.04 0.06 0.07 0.04 Na₂O 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.16 K2O 0.51 0.43 0.48 0.29 0.47 0.49 0.52 0.51 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 95.11 94.92 95.13 94.90 95.09 94.95 95.02 95.14 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.41 3.45 1.73 4.32 1.95 1.86 2.26 2.73 AR 1.79 1.76 1.14 1.72 1.54 1.20 1.36 1.46 C₃S% 57.45 64.68 53.39 69.27 54.01 56.39 57.61 61.85 clinker C₂S% 20.04 18.50 19.22 17.07 20.19 18.11 19.32 18.22 phases C₃A% 10.02 7.32 7.48 5.89 10.28 7.63 7.84 7.35 C₄AF% 10.03 7.49 17.09 6.27 13.06 15.75 12.49 10.23 H.M. 2.12 2.24 1.97 2.31 2.03 2.01 2.08 2.16 clinker M.B.T 1426.73 1501.08 1328.91 1542.28 1372.33 1358.77 1402.70 1452.16 properties B.I 2.94 4.48 2.22 5.85 2.37 2.47 2.84 3.52 L.Ph. 27.50 20.53 34.65 16.72 31.94 32.27 28.66 24.64 20

Appendices

Continued….E Requirments H1+C1 H1+C2 H1+C3 H1+C4 H1+C5 H1+C6 H1+C7 H1+C8 X= 0.297 0.220 0.300 0.191 0.281 0.362 0.425 0.238 Y= 0.703 0.780 0.700 0.809 0.719 0.638 0.575 0.762 SiO₂ 13.67 14.38 13.17 14.76 13.18 13.19 14.11 13.87 Al₂O₃ 3.94 3.09 4.32 2.65 4.36 4.10 3.85 3.40 Fe₂O₃ 2.75 2.35 4.15 2.16 3.33 3.79 3.20 2.84 Raw mix CaO 41.76 42.46 41.38 43.14 41.13 41.31 43.01 41.86 MgO 1.11 0.91 1.35 0.70 1.14 0.90 1.22 1.00 SO₃ 0.02 0.01 0.02 0.01 0.02 0.03 0.04 0.02 Na₂O 0.04 0.04 0.05 0.03 0.04 0.05 0.13 0.09 K2O 0.30 0.25 0.29 0.17 0.28 0.29 0.32 0.29 L.O.I 36.10 36.11 34.90 35.95 36.15 36.00 33.83 36.25 ToTal 99.64 99.60 99.63 99.59 99.62 99.66 99.71 99.61 SiO₂ 21.51 22.65 20.35 23.19 20.76 20.72 21.43 21.89 Al₂O₃ 6.20 4.86 6.68 4.17 6.87 6.45 5.85 5.36 Fe₂O₃ 4.33 3.71 6.41 3.39 5.25 5.95 4.85 4.48 Clinker CaO 65.72 66.87 63.92 67.80 64.80 64.89 65.29 66.07 MgO 1.74 1.44 2.09 1.10 1.79 1.42 1.85 1.57 SO₃ 0.03 0.02 0.02 0.02 0.03 0.04 0.05 0.03 Na₂O 0.07 0.06 0.08 0.05 0.06 0.07 0.19 0.14 K2O 0.47 0.39 0.45 0.27 0.44 0.46 0.49 0.47 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.07 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 95.11 94.81 94.70 95.11 94.77 94.74 95.02 95.21 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.04 2.64 1.55 3.07 1.71 1.67 2.00 2.22 AR 1.43 1.31 1.04 1.23 1.31 1.08 1.20 1.20 C₃S% 56.17 62.07 51.48 66.83 52.26 54.76 56.57 60.10 clinker C₂S% 19.28 18.12 19.50 16.08 20.10 18.09 18.76 17.41 phases C₃A% 9.10 6.60 6.85 5.30 9.32 7.03 7.28 6.63 C₄AF% 13.19 11.28 19.51 10.33 15.99 18.09 14.77 13.63 H.M. 2.05 2.14 1.91 2.20 1.97 1.96 2.03 2.08 clinker M.B.T 1384.61 1444.21 1292.16 1482.45 1331.02 1324.14 1371.18 1404.04 properties B.I 2.58 3.56 2.00 4.38 2.12 2.23 2.57 2.97 L.Ph. 30.66 24.83 37.10 21.58 34.75 34.71 31.05 28.36 21

Appendices

Continued….E Requirments H2+C1 H2+C2 H2+C3 H2+C4 H2+C5 H2+C6 H2+C7 H2+C8 X= 0.333 0.249 0.336 0.218 0.316 0.400 0.466 0.270 Y= 0.667 0.751 0.664 0.782 0.684 0.600 0.534 0.730 SiO₂ 14.13 14.95 13.56 15.47 13.58 13.55 14.52 14.43 Al₂O₃ 3.75 2.74 4.17 2.24 4.21 3.95 3.69 3.12 Fe₂O₃ 2.10 1.56 3.67 1.31 2.74 3.31 2.72 2.14 Raw mix CaO 42.29 43.20 41.87 43.95 41.61 41.75 43.56 42.43 MgO 1.12 0.90 1.40 0.66 1.16 0.89 1.24 1.00 SO₃ 0.02 0.02 0.02 0.02 0.03 0.04 0.04 0.03 Na₂O 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 K2O 0.33 0.27 0.32 0.19 0.30 0.32 0.35 0.33 L.O.I 36.46 36.55 35.13 36.36 36.54 36.32 33.91 36.66 ToTal 100.21 100.23 100.20 100.23 100.20 100.18 100.17 100.23 SiO₂ 22.17 23.47 20.84 24.21 21.33 21.22 21.92 22.70 Al₂O₃ 5.88 4.30 6.41 3.51 6.61 6.18 5.56 4.90 Fe₂O₃ 3.30 2.45 5.64 2.05 4.30 5.19 4.10 3.36 Clinker CaO 66.34 67.83 64.35 68.80 65.36 65.38 65.74 66.75 MgO 1.76 1.41 2.15 1.03 1.81 1.40 1.87 1.57 SO₃ 0.04 0.03 0.04 0.04 0.04 0.06 0.07 0.05 Na₂O 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.16 K2O 0.51 0.43 0.49 0.29 0.47 0.50 0.52 0.51 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.07 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 94.93 95.06 94.61 94.87 94.71 94.64 94.94 94.84 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.42 3.47 1.73 4.35 1.95 1.87 2.27 2.75 AR 1.78 1.75 1.14 1.71 1.54 1.19 1.36 1.46 C₃S% 57.27 65.27 52.33 69.48 53.29 55.83 57.59 61.36 clinker C₂S% 20.36 18.05 20.28 17.00 20.94 18.71 19.40 18.78 phases C₃A% 10.00 7.25 7.46 5.83 10.25 7.60 7.80 7.30 C₄AF% 10.04 7.46 17.15 6.25 13.08 15.78 12.48 10.24 H.M. 2.12 2.24 1.96 2.31 2.03 2.01 2.08 2.16 clinker M.B.T 1425.95 1504.38 1323.44 1543.73 1368.87 1355.95 1402.78 1450.05 properties B.I 2.93 4.55 2.18 5.91 2.34 2.44 2.84 3.50 L.Ph. 27.44 20.36 34.68 16.57 31.91 32.24 28.59 24.56 22

Appendices

Continued…E Requirments H3+C1 H3+C2 H3+C3 H3+C4 H3+C5 H3+C6 H3+C7 H3+C8 X= 0.307 0.228 0.310 0.199 0.291 0.373 0.437 0.247 Y= 0.693 0.772 0.690 0.801 0.709 0.627 0.563 0.753 SiO₂ 13.76 14.50 13.25 14.95 13.26 13.26 14.21 14.01 Al₂O₃ 4.00 3.12 4.40 2.68 4.44 4.17 3.90 3.45 Fe₂O₃ 2.53 2.09 3.97 1.88 3.12 3.61 3.03 2.60 Raw mix CaO 41.79 42.53 41.40 43.21 41.14 41.33 43.06 41.87 MgO 1.31 1.13 1.56 0.92 1.35 1.08 1.39 1.21 SO₃ 0.04 0.04 0.04 0.04 0.05 0.05 0.06 0.05 Na₂O 0.04 0.04 0.05 0.04 0.04 0.05 0.13 0.09 K2O 0.32 0.27 0.31 0.19 0.29 0.31 0.34 0.31 L.O.I 35.94 35.94 34.70 35.75 35.99 35.85 33.64 36.07 ToTal 99.69 99.65 99.69 99.65 99.68 99.71 99.75 99.67 SiO₂ 21.58 22.76 20.39 23.39 20.82 20.77 21.50 22.02 Al₂O₃ 6.28 4.90 6.77 4.19 6.97 6.53 5.90 5.43 Fe₂O₃ 3.97 3.27 6.11 2.94 4.91 5.66 4.58 4.09 Clinker CaO 65.56 66.75 63.70 67.62 64.60 64.71 65.13 65.84 MgO 2.05 1.77 2.41 1.44 2.11 1.69 2.10 1.91 SO₃ 0.07 0.07 0.07 0.07 0.07 0.08 0.09 0.08 Na₂O 0.07 0.06 0.08 0.06 0.06 0.08 0.20 0.14 K2O 0.50 0.42 0.47 0.29 0.46 0.48 0.51 0.49 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.07 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 95.14 94.89 94.68 94.84 94.76 94.71 94.96 94.98 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.11 2.79 1.58 3.28 1.75 1.70 2.05 2.32 AR 1.58 1.50 1.11 1.43 1.42 1.15 1.29 1.33 C₃S% 54.86 60.96 49.96 64.96 50.71 53.42 55.33 58.17 clinker C₂S% 20.48 19.27 20.77 18.06 21.43 19.25 19.89 19.26 phases C₃A% 9.93 7.44 7.60 6.14 10.18 7.72 7.89 7.47 C₄AF% 12.07 9.96 18.60 8.94 14.93 17.22 13.93 12.43 H.M. 2.06 2.16 1.91 2.22 1.98 1.96 2.04 2.09 clinker M.B.T 1389.85 1452.77 1293.97 1488.42 1334.24 1326.60 1373.91 1407.28 properties B.I 2.56 3.59 1.95 4.42 2.07 2.19 2.54 2.92 L.Ph. 30.44 24.38 37.09 21.04 34.66 34.64 30.90 28.09 23

Appendices

Continued…E Requirments Bn1+C1 Bn1+C2 Bn1+C3 Bn1+C4 Bn1+C5 Bn1+C6 Bn1+C7 Bn1+C8 X= 0.327 0.244 0.330 0.214 0.310 0.394 0.459 0.264 Y= 0.673 0.756 0.670 0.786 0.690 0.606 0.541 0.736 SiO₂ 13.95 14.73 13.36 15.25 13.38 13.36 14.37 14.19 Al₂O₃ 3.79 2.81 4.19 2.32 4.24 3.97 3.72 3.17 Fe₂O₃ 2.15 1.63 3.68 1.39 2.77 3.33 2.75 2.19 Raw mix CaO 41.77 42.59 41.40 43.29 41.12 41.33 43.13 41.89 MgO 1.32 1.12 1.58 0.90 1.35 1.07 1.40 1.21 SO₃ 0.03 0.03 0.03 0.03 0.03 0.04 0.05 0.04 Na₂O 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 K2O 0.33 0.28 0.32 0.19 0.30 0.32 0.35 0.33 L.O.I 36.33 36.40 35.05 36.19 36.42 36.23 33.85 36.53 ToTal 99.71 99.62 99.67 99.61 99.66 99.70 99.73 99.63 SiO₂ 22.01 23.30 20.67 24.06 21.16 21.05 21.80 22.48 Al₂O₃ 5.98 4.44 6.49 3.67 6.70 6.25 5.64 5.02 Fe₂O₃ 3.40 2.58 5.69 2.19 4.38 5.24 4.17 3.46 Clinker CaO 65.90 67.37 64.07 68.27 65.03 65.13 65.46 66.39 MgO 2.08 1.78 2.45 1.41 2.14 1.69 2.12 1.92 SO₃ 0.05 0.04 0.05 0.05 0.05 0.07 0.07 0.06 Na₂O 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.16 K2O 0.52 0.44 0.49 0.30 0.48 0.50 0.52 0.52 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 94.99 95.11 95.01 94.74 95.01 95.05 95.05 95.22 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.35 3.32 1.70 4.11 1.91 1.83 2.22 2.65 AR 1.76 1.72 1.14 1.67 1.53 1.19 1.35 1.45 C₃S% 55.85 63.57 51.85 67.20 52.51 55.47 56.68 60.57 clinker C₂S% 20.98 18.84 20.15 18.27 21.05 18.50 19.75 18.77 phases C₃A% 9.56 7.01 7.00 5.68 9.74 7.15 7.89 7.43 C₄AF% 10.34 7.84 17.33 6.66 13.33 15.95 12.69 10.54 H.M. 2.10 2.22 1.95 2.28 2.02 2.00 2.07 2.14 clinker M.B.T 1303.79 1364.28 1214.98 1393.18 1256.80 1240.86 1282.34 1320.95 properties B.I 2.81 4.28 2.13 5.44 2.28 2.40 2.75 3.37 L.Ph. 28.28 21.43 35.36 17.75 32.69 32.89 29.23 25.49 24

Appendices

Continued…E Requirments Bn2+C1 Bn2+C2 Bn2+C3 Bn2+C4 Bn2+C5 Bn2+C6 Bn2+C7 Bn2+C8 X= 0.327 0.244 0.330 0.213 0.310 0.394 0.459 0.264 Y= 0.673 0.756 0.670 0.787 0.690 0.606 0.541 0.736 SiO₂ 13.99 14.78 13.40 15.23 13.42 13.39 14.40 14.23 Al₂O₃ 3.83 2.85 4.24 2.36 4.28 4.01 3.75 3.21 Fe₂O₃ 2.10 1.57 3.63 1.32 2.72 3.28 2.70 2.13 Raw mix CaO 42.00 42.86 41.64 43.62 41.36 41.55 43.31 42.15 MgO 1.13 0.91 1.40 0.67 1.16 0.90 1.24 1.00 SO₃ 0.06 0.06 0.06 0.06 0.06 0.07 0.07 0.06 Na₂O 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 K2O 0.34 0.29 0.33 0.21 0.32 0.33 0.36 0.34 L.O.I 36.38 36.46 35.10 36.29 36.47 36.28 33.89 36.59 ToTal 99.88 99.81 99.83 99.80 99.83 99.85 99.86 99.82 SiO₂ 22.04 23.32 20.70 23.98 21.18 21.07 21.82 22.51 Al₂O₃ 6.03 4.50 6.54 3.72 6.75 6.30 5.68 5.08 Fe₂O₃ 3.31 2.47 5.60 2.08 4.29 5.16 4.10 3.36 Clinker CaO 66.15 67.65 64.32 68.68 65.29 65.35 65.65 66.66 MgO 1.78 1.44 2.16 1.06 1.83 1.42 1.89 1.59 SO₃ 0.09 0.09 0.09 0.10 0.10 0.10 0.11 0.10 Na₂O 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.16 K2O 0.54 0.46 0.51 0.32 0.50 0.52 0.54 0.54 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 94.93 95.04 94.95 95.22 94.95 95.00 95.01 95.16 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.36 3.34 1.70 4.14 1.92 1.84 2.23 2.67 AR 1.82 1.82 1.17 1.79 1.57 1.22 1.39 1.51 C₃S% 56.35 64.11 52.34 69.11 53.02 55.92 57.07 61.11 clinker C₂S% 20.67 18.50 19.85 16.62 20.73 18.23 19.52 18.44 phases C₃A% 9.85 7.34 7.28 6.01 10.04 7.41 8.12 7.76 C₄AF% 10.06 7.53 17.04 6.32 13.04 15.69 12.47 10.24 H.M. 2.11 2.23 1.96 2.31 2.03 2.01 2.08 2.15 clinker M.B.T 1307.46 1368.29 1218.72 1401.06 1260.66 1244.26 1285.20 1324.93 properties B.I 2.83 4.31 2.15 5.60 2.30 2.42 2.77 3.39 L.Ph. 28.00 21.12 35.07 17.37 32.39 32.62 29.01 25.19 25

Appendices

Continued…E Requirments Bn3+C1 Bn3+C2 Bn3+C3 Bn3+C4 Bn3+C5 Bn3+C6 Bn3+C7 Bn3+C8 X= 0.322 0.240 0.325 0.210 0.305 0.389 0.454 0.260 Y= 0.678 0.760 0.675 0.790 0.695 0.611 0.546 0.740 SiO₂ 13.97 14.75 13.43 15.24 13.44 13.43 14.40 14.23 Al₂O₃ 3.85 2.89 4.26 2.42 4.30 4.03 3.77 3.25 Fe₂O₃ 2.26 1.76 3.78 1.53 2.88 3.42 2.83 2.31 Raw mix CaO 42.12 42.96 41.70 43.67 41.44 41.60 43.37 42.25 MgO 1.14 0.93 1.40 0.69 1.17 0.91 1.25 1.02 SO₃ 0.04 0.04 0.04 0.05 0.05 0.05 0.06 0.05 Na₂O 0.05 0.04 0.06 0.04 0.04 0.05 0.14 0.10 K2O 0.36 0.31 0.35 0.23 0.33 0.34 0.37 0.36 L.O.I 35.88 35.88 34.58 35.67 35.93 35.80 33.50 36.02 ToTal 99.61 99.57 99.61 99.54 99.59 99.65 99.69 99.58 SiO₂ 21.92 23.16 20.65 23.86 21.12 21.03 21.75 22.38 Al₂O₃ 6.04 4.54 6.55 3.79 6.76 6.32 5.70 5.11 Fe₂O₃ 3.55 2.77 5.81 2.40 4.53 5.36 4.28 3.64 Clinker CaO 66.08 67.46 64.14 68.38 65.10 65.15 65.53 66.48 MgO 1.78 1.45 2.16 1.09 1.84 1.43 1.89 1.60 SO₃ 0.07 0.07 0.07 0.07 0.07 0.08 0.09 0.08 Na₂O 0.07 0.06 0.09 0.06 0.06 0.08 0.21 0.15 K2O 0.56 0.49 0.53 0.36 0.52 0.54 0.56 0.56 L.O.I 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ToTal 100.07 100.00 100.00 100.00 100.00 100.00 100.00 100.00 LSF* 95.05 95.08 94.65 94.90 94.72 94.66 94.93 95.10 LSF** 95.00 95.00 95.00 95.00 95.00 95.00 95.00 95.00 Ratio SR 2.29 3.17 1.67 3.86 1.87 1.80 2.18 2.56 AR 1.70 1.64 1.13 1.58 1.49 1.18 1.33 1.40 C₃S% 56.59 63.96 51.59 67.96 52.45 55.04 56.81 60.78 clinker C₂S% 20.15 18.15 20.29 17.14 20.98 18.79 19.50 18.33 phases C₃A% 9.99 7.35 7.54 5.98 10.24 7.67 7.85 7.38 C₄AF% 10.81 8.43 17.68 7.29 13.78 16.31 13.03 11.06 H.M. 2.10 2.21 1.94 2.28 2.01 1.99 2.07 2.14 clinker M.B.T 1298.07 1356.54 1207.79 1386.01 1249.17 1233.29 1278.55 1315.09 properties B.I 2.72 4.05 2.05 5.12 2.18 2.29 2.72 3.29 L.Ph. 28.59 21.92 35.58 18.33 32.96 33.15 29.47 25.90

26

Appendices

Appendix (F) Iraqi standard specification (IQS). No.31 (1981) for measurement of Bulk density, Specific gravity, moisture content, apparent porosity, and Water absorption of limestone rock for production of Portland cement. The procedure according to IQS. Use 46 samples of limestone 1- Dry the samples at temperature 150 °C in the oven for 5 hours then put them in the desiccators for cooling. Weigh the samples directly to accuracy 0.01gm; this is a dry weight (D). 2- Put the samples in water (Tank), without any contact between the tank and samples. Heat the water to boiling point for 5 hours, and then allow cooling at room temperature for 24hours. Remove the sample from the water then weigh the hanged sample in water; this is suspended weight (S). 3- Remove the samples and wipe the surface water with a damp cloth and weigh the sample, this is saturated weight (M).

Exterior volume (V) = M-S Apparent porosity (P) % = [(M-D)/V] * 100 Water absorption (A) % = [(M-D)/D] * 100 Bulk density (B) = D/V gm/cm3

27

Appendices

Appendix (G) ISRM 1985. Suggested method for determining point-load strength. Int. J. Rock Mech. Min. Sci. Geomech. Abstr. 22, pp. 53–60. The test was performed according to the procedure of ISRM (1985), in which the point load strength allows the determination of the uncorrected point load strength index (Is), which can be derived as follows: Is = F / De2= ᴨ F/4A = ᴨ F/4*D*W Where: Is: Uncorrected point load strength index, in MPa or psi F: Force at failure De: Equivalent core diameter, in mm or inches which is given by: 1-De = D for diametric tests 2-De = √ (4A/ᴨ) for axial, block or irregular tests, (Fig, 4.2). Where: A=D*W A: is minimum cross sectional area of a plane through the platen contact points. D: is the thickness of specimen and W: is the horizontal width of specimen. This index must be corrected to the standard equivalent diameter (De) of 50 mm as follows: Is50 = f *(F/De2) = f * Is………………ISRM (1985) Where: Is50: point load strength index of a specimen of 50mm diameter. f: size correction factor calculated as: f = (De/ 50)0.45 Bieniawski (1975) suggests the following approximate relation between UCS, Is, and the core diameter (D). UCS = (14+0.175D) * Is50 Where: Is50 = point load strength index of a specimen of 50 mm diameter. UCS = (14+0.17*50) *Is50 = 22.5* Is50

28

Appendices

Specimen shape requirements for (a) the diametrical test. (b) The axial test, and (c) block test and (d) irregular lump test (ISRM 1985). The purpose of this test to find uniaxial compressive strength for engineering classification of rocks

29

‫تقيم حجر الجيري في تكوين أفرومان‬ ‫لصناعة األسمنت البورتالندي‪ ,‬منطقة الهمبجة‬ ‫في جنوب الشرق منطقة السميمانية‪ ،‬اقميم كوردستان‬ ‫شمال الشرق – العراق‬ ‫رسانة‬ ‫يقدية إنى يجهس فاكهتي انعهوو و تربية انعهوو‪،‬‬ ‫سكول انعهوو‪ ،‬جايعة انسهيًانية‬ ‫كجسء ين يتطهبات نيم درجة ياجستيرعهوو‬ ‫في عهى االرض‬

‫ين قبم‬ ‫جرو محمد فتاح أمين‬ ‫بكالوريوس جيولوجي ( ‪ ،)6002‬جامعة السميمانية‬

‫بأشراف‬ ‫د‪ .‬تونة أحًد ييرزا يحًد‬ ‫و‪ .‬أستاد‬

‫تشرين األول‪ 6063‬م‬

‫محرم‪ 6342‬ه‬

‫‪30‬‬

‫المستخمص‬ ‫يتضمن ىذا البحث تقييم الحجر الجيري لتكوين أفرومان ( الترياسي أألعمى) كمادة خام محتممة لصناعة‬

‫االسمنت البورتالندي ‪ .‬شممت منطقة الدراسةجبمي أفرومان وسورين الواقعين في منطقة حمبجة في اقميم كردستان‬ ‫العراق‪.‬يمتد ىذان الجبالن من الشمال الغربي الى شمال شرق مدينة خورمال بين خطي طول ("‪46° 00´ 36‬و ´‪05‬‬ ‫‪ )50" 46°‬شرقاًوخطي عرض( "‪ 35° 17´ 02‬و "‪ ( 35° 20´ 50‬شماالً ‪ .‬قسمت منطقة الدراسة الى اربعة مقاطع‬ ‫عرضية وىي( ‪ : A‬أحمد اوه ) و (‪ : Sh‬وادي شاناو) و ( ‪ :H‬ىيالنبي ) و (‪ : Bn‬وادي بانيشار)‪ .‬تظمنت ىذه‬ ‫الدراسة الوصف الحقمي والتحاليل البصرية والمعدنية والجيوكيميائية ودراسة الخصائص الفيزياوية والميكانيكية لمصخور‬

‫فيالمقاطع العرضية أألربعة لغرض تقييم تكوين أفرومان‪.‬‬ ‫الدراسة الحقمية بينت بان تكوين افرومان ىو من الحجر الجيري النقي وال يحتوي عمى اي تتابعات او طبقات‬ ‫من الحجر الجيري المارلي‪ .‬الحجر الجيري عمى العموم ذو لون رمادي وكتمي وصمب ويحتوي عمى كسور وفواصل ‪,‬‬ ‫كما تبين من خالل الدراسة البصرية وجود متجرات كبيرة ثنائية المفصل وجدت في وادي بانيشارمثل‬

‫(‪.)Megalodone‬‬

‫تم تمييز ستة سحنات دقيقة في المقاطع أألربعة المدروسة وىي‪:‬‬ ‫‪(Mudstone, wackstone, lithoclastic packstone, oolitic packstone to grainstone, lithoclastic‬‬ ‫)‪bioclastic grainstone and peloidal grainstone.‬‬

‫المتحجرات ىي نادرة نسبيا ولكن تم تحديد بعض المتحجرات الدقيقة‬

‫مثل‪ ،Plecypod .)Echinoid‬وبعض‬

‫ال‪bioclast‬الغير معروفة) ‪ ،‬و تبين بصرياً أن الكالسيت ىو في طور الييمنة المعدنية‪.‬‬

‫التحميل المعدني باستخدام ‪ XRD‬يدل عمى أن الكالسيت ىو المعدن المييمن في عينات الحجر الجيري يميو الكوارتز‬

‫وبشكل قميل وكمية قميمة من الدولوميت‪.‬‬

‫الدراسة المعدنية لمطين بينت بأنو يحتوي عمى معادن طينية وغير طينية‬

‫‪ .‬تمثمت المعادن الطينية‬

‫بألكموريت كمعدن سائد ويميو اإلاليت والمونتموريمينايت والكاولينايت‪ ,‬اما المعادن الغير طينيييي الكوارتز كمعدن سائد‬ ‫ا‬ ‫يميو الكالسايت ونسبة قميمة جدا من البالجيوكيز‪ .‬البقايا الغير ذائبة (المعادنالغير كاربوناتية) في الحجر الجيري ىي‬ ‫الكوارتز‪ ،‬والمعادن الطينية وأكاسيد الحديد مثل الييماتايتوالبايرايت‪.‬‬ ‫الدراسة الجيوكيميائية لمحجر الجيري لتكوين افرومان بينت بأن جميع أألكاسيد الرئيسة والثانوية مثل(‪CaO‬و‬

‫‪ SiO₂‬و‪ Al₂O₃‬و‪ Fe₂O₃‬و ‪ MgO‬و‪ SO₃‬و ‪ P₂O5‬و‪ TiO₂‬و ‪ MnO‬و(ىي ضمن المواصفات القياسية لتصنيع‬ ‫سمنت البورتالند‪ .‬والتى تتطمبالنسبة العالية لكاربونات الكالسيوم في الحجر الجيري والبالغة ‪ %79‬في صخورمنطقة‬ ‫الدراسة وتم خمطيا مع أألطيان المتوفرة في منطقة الدراسة ألنتاج سمنت بورتالندي عالي التشبع بالكالسيوم مع تعديل‬ ‫نسب السميكا واأللمنيوم‪ .‬تم استخدام معامل تشبع الحجر الجيري ‪ 70‬و ‪ 79‬لتقدير نسبة خمط كل من الحجر الجيري‬

‫والطين و بنسب مختمفة لتقدير تركيب الكمنكر‪ .‬تركيب الكمنكر المقدروأألطوار المعدنية المحسوبة لألاليت والبياليت‬ ‫واأللومينايت والفيرايت بينت بأنيا متوافقة مع المواصفات القياسية إلنتاج األسمنت البورتالندي‪ .‬نتائج مقارنة نسب‬ ‫السميكا واأللمنيوم وكذلك الوحدات الييدروليكية ودرجة ح اررة أألحتراق القصوى ودليل قابمية أألحتراق والطور السائل‬ ‫لمعينات المدروسة المتفقة مع المواصفات القياسية الخاصة لألسمنت البورتالندي‬

‫المدروسةمتفقة مع ىذه المعايير‪.‬‬

‫‪31‬‬

‫تظير بأن معظم العينات‬

‫الخصائص الفيزيائية (المسامية الظاىرية و الكثافة الكمية والجاذبية النوعية الظاىرية‬

‫ومحتوى الرطوبة‬

‫الطبيعية وامتصاص الماء) بينت أن معظم العينات المدروسة تقع ضمن النطاقات الطبيعية لصخور الكاربونات‬ ‫المستخدمة في صناعة االسمنت‪ .‬ومن خالل نتائج قوة الضغط النطاقات عينات الدراسة أشارت إلى أن تصنف معظم‬ ‫عينات معتدلة إلى قوية قوية جدا ‪ .‬تصنيف الرواسب سيمسيكالستيك يظير ذلك‪ ،‬وعينات من التربة من منطقة‬ ‫الدراسة ىي أحجار الطين الرممي إال عينة ‪ C3‬ىو الحجر الرممي الطيني‪.‬‬ ‫‪.‬‬

‫‪32‬‬

‫يةهَطةنطاندنى بةزدى كوطى ثيَلًاتووى يةوزاماى‬ ‫ب َو ثيػةضاشى ضينةنتوَى ثوَزتالند‪ ,‬ناوضةى يةهَةجبة‬ ‫هةباغوزى ِزوَذيةآلتي ناوضةى ضويَنانى‪,‬يةزيَنى كوزدضتاى‬ ‫باكوزى ِزوَذيةآلتي ‪ -‬عيَساق‬

‫نامةيةكة‬ ‫ثيَػلةؽ كساوة بة ئةجنومةنى فاكةهَتى شانطت و ثةزوةزدة شانطتةكاى‬ ‫ضلوهَى شانطت هة شانلوى ضويَنانى‬ ‫وةن بة غيَم هة ثيَداويطتيةكانى بة دةضتًيَهانى بسِوانامةى‬ ‫ثوةى ماضتةز هة شانطتى‬ ‫شةويهاضى دا‬

‫هةاليةى‬ ‫ضسوَ حمند فتاح أمني‬ ‫بلاهوزيوَع هة شةويهاضى دا ( ‪ ،)6002‬شانلوَى ضويَنانى‬

‫بة ضةزثةزغتى‬ ‫د‪.‬توهَة أمحد مريشا حمند‬ ‫ى‪ .‬ثسوَفيطوَز‬

‫تشرينى يةكةم ‪ 6063‬شايهى‬

‫طةهَازِيَصاى ‪ 6172‬كوزدى‬ ‫‪1‬‬

‫ثوختة‬ ‫هةم هيَل َوهَيهةوةيةدا يةوهَدزاوة بةزدى كوطيى ثيَلًاتةى يةوزاماى ( تساياضيلى دزةنط) هةزِووى تواناى ئةم بةزدانة‬ ‫وةن مادةى خام بوَ ثيػةضاشى ضينةنتوَى ثوَزتالند يةهَبطةنطيَهدزيَت‪ .‬ناوضةى تويَريهةوةكة بسيتيية هة غاخةكانى ضووزيَو و‬ ‫يةوزاماى كةدةكةونة ثازيَصطاى يةهَةجبة هة يةزيَنى كوزدضتاى هة باكووزى خوَزيةالَتى عيَساق‪ .‬ئةم غاخة هةباكووزى خوَزئاوا‬ ‫بوَ باكووزى خوَزيةالَتى غازوَضلةى خوزمالَ دزيَردةبيَتةوة كة ضهووزى ناوضةى تويَريهةوة بسيتيية هة ي َيوَةكانى دزيَرى " ‪46°‬‬ ‫‪ 00´ 36‬و "‪ 46° 05' 50‬خوَزيةالَت و ي َيوَةكانى ثانى "‪ 35° 17' 02‬و "‪ 35° 20' 50‬باكووز‪ .‬ناوضةكة بوَ ضواز زِيَسِةو‬ ‫دابةغلساوة كةئةوانيؼ ئةمحةد ئاوا ( ‪ ) A‬و د َوهَى غةناو ( ‪ )Sh‬و ييَالنجى ( ‪ ) H‬و د َوهَى بانيػاز ( ‪ ) Bn‬ى‪ .‬ئةم‬ ‫هيَلوَهَيهةوة تيَيدا باضى وةضفلسدنى مةيدانى و ثيرتوَطسافى و غيلازى خاوةكاى و غيلازى جيوَكينيايى و زِةوغتة فيصيايى و‬ ‫ميلانيلييةكانى هةيةزضواز زِيَسِةوةكةدا هةثيَهاو يةهَطةنطاندنى ثيَلًاتةى يةوزاماى باع كساوة‪.‬‬ ‫وةضفلسدنى مةيدانى ( ك َيوَطةيى) ثيػانيدا كة ئةم ثيَلًاتةية هةزِووى بةزدشانييةوة ثيَم ديَت هة بةزدى كوطى ثان‬ ‫و ييض ضيهيَلى بةزدى كوطى قوزِيى نةبيهساوة‪ .‬ئةم ضيهانة بةطػتى زِةنط خ َوهَةميَػني و بازضتةيني و زِةقو و دزش و‬ ‫هيَلرتاشانياى تيَداية‪ ,‬ئةمة ضةزةزِاى ئةوةى كةهةد َوهَى بانيػاز شوَزيَم هة بةزديهةى دووهةثلى طةوزةى وةن ميطاهودوَى‬ ‫توَمازكساوة‪ .‬هةزِووى بةزدشانييةوة غةؽ غيَواشى وزد هةيةز ضواز زِيَسِةوةكة جياكساونةتةوة كة ئةوانيؼ بسيتيني هة بةزدى‬ ‫قوزِيو و ثيطةبةزد و ثاكطتوَنى ثازضةيى و ثاكطتوَنى ئوَئوَهيتى – بةزدى دةنل َوهَةيى و بةزدى دةنل َوهَيى ثازضةيى بةزديهةى و‬ ‫بةزدى دةنل َوهَةيى ثيووَيدى‪ .‬بةزديهةكاى بة طػتى شوَزكةمو يةزضةندة ضةند ثازضةيةكى وةن ئيليهوَيد و دووهةثلةكاى و‬ ‫فوَزاميهيفيَسا جياكساونةتةوة‪ ,‬ضةزةزِاى يةنديَم ثازضةى نةناضساوة‪ .‬هيَلوَهَيهةوةى مايلسوَضلوَثى دةزخيطت كة خاوى كاهطايت‬ ‫خاوى ضةزةكيية هة بةزدةكاندا‪.‬‬ ‫غيلازى خاويى بةبةكازييَهانى ئاميَسى تيػلى ئيَلطى ثةزضبووةوةدةزخيطت كة خاوى كاهطايت خاوى شاهَة هة منوونة‬ ‫كوطييةكاندا‪ ,‬هةثاؽ ئةو كوزاتص شوَز بةكةمى و كةميَم د َو َهوَمايت يةى‪ .‬غيلازكسدنى بةزدةقوزِييةكاى دةزخيطت كة ثيَلديَو هة‬ ‫خاوة قوزِييةكاى و خاوة ناقوزِييةكاى‪ .‬خاوة قوزِييةكاى بسيتيني هة كووَزايت وةن خاويَلى شالَ‪ ,‬ثاغاى خاوةكانى ئياليت و‬ ‫موَنتنوَزهوَنتيت و كائوَهيهايت ديَو‪ .‬يةزضى خاوة ناقوزِييةكانة بسيتيني هة كوازتص بةغيَوةيةكى شالَ و ثاغاى كاهطايت و‬ ‫زِيَرةيةكى كةمى ثالجيوَكويَص‪ .‬ثامشاوةى نةتواوةى( خاوة ناكوطييةكاى)‬

‫ناو بةزدةكانى كوظ بسيتيني هة كوازتص و خاوة‬

‫قوزِييةكاى و ئوَكطيدةكانى ئاضهى وةن ييناتايت و ثايسايت‪.‬‬ ‫هيَلوَهَيهةوةى جيوَكينيايى بوَ بةزدةكوطةكانى ثيَلًاتةى يةوزاماى ثيػانى دةدات كة زِيَرةى طػت ئوَكطيدةكانى‬ ‫ضةزةكى و ناضةزةكييةكاى هةضهووزى ضتاندةزداية بوَ ثيػةضاشى ضينةنتوَى ثوَزتالند‪ .‬زِيَرةى بةزشى كازبوَناتى كاهطيوَم‬ ‫هةبةزدةكوطةكاندا نصيلةى ‪ %71‬كة ثيَويطتة هةطةلَ قوزِى ناوضةكةدا تيَلةلَ بلسيَت بوَ دزوضتلسدنى ضينةنتوَى ثوَزتالند كة‬ ‫ياوكوَهلةى تيَسى بةزدةكوطى بةزشة و زِيَرةى ضويلا و ئةهوَميها زِيَلدساوة‪ .‬ياوكوَهلةى تيَسى بةزدةكوطى ‪ 70‬و ‪79‬‬ ‫بةكازييَهساوة بوَ خةمالَندنى زِيَرةى تيَلةهَةى بةزدى كوظ و مادةى قوزِةكة بة زِيَرةى جياواش و ثاغاى خةمالَندنى ثيَلًاتةى‬ ‫كويهلةزةكة‪.‬ثيَلًاتةى كويهلةزى خةموَيَهساو و ئةذمازكسدنى قوَناغ خاوةكانى ئةاليت و بياليت ئةهوميهةيت و فيَسايت ثيػانى‬ ‫دةدات كة طوجناوى هةطةلَ ضهووزى ضتاندازدى ثيػةضاشى ضينةنتوَى ثوَزتالند‪ .‬بةزاوزدكسدنى ئةجنامةكانى زِيَرةى ضويلا و‬ ‫ئةهوميها يةزوةيا موَديوهةضى يايدزوَهيلى و بةزشتسيو ثوةى طةزمى تواناى ضووتاندى و ياوكوَهلةى تواناى ضووتاندى و‬ ‫قوَناغى غوى منوونةكاى هةطةلَ ضهووزى ضتاندازدةكانى ثيػةضاشى ضينةنتوَى ثوَزتالند ثيػانى ئةدات كة شوزتسيهةى‬ ‫منوونةكاى هةطةلَ ئةم ضتاندازدانة دا طوجناوة‪.‬‬ ‫‪34‬‬

‫زِةوغتة فيصياييةكانى وةن كونوَضلةيَتى زِواهَةتيى و ضسِيى طػتى و كيَػى جوَزيى زِواهَةتيى و زِيَرةى غيَى ضسوغتى‬ ‫و مريهى ئاو ثيػانى ئةدات كة شوَزيهةى منوونةكاى هة مةوداى طوجناوداى بوَ بةزدى كوطيى كة هة ثيػةضاشى ضينةنتوَدا‬ ‫بةكازبيَو‪ .‬ئةمة ضةزةزِاى ئةوةى نصمى غيَى منوونةكاى ثيػانى ئةدات كة ثسوَضةى وغم دةكسيَت بةكازبًيَهسيَت‬ ‫بوَبةزيةمًيَهانى ثيػةضاشى ضينةنتوَ هةم بةزدانة‪ .‬هةو ئةجنامةى دةضتناى كةوتووة هة بةزطسى ثةضتاوتهى منونةكاى‬ ‫مةوداكةى ئةوة دةزدةخات كة شوَزبةى منونةكاى ثوَهيَهى ب َو كساوة هة بةييَصييةكى مام ناوةند بوَ بةييَصييةكى شوَز‪ .‬ثوَهيَهلسدنى‬ ‫نيػتووة ثازضةييةكاندا ئةوةثيػاى ئةدات كة منوونة خاكييةكاى هةناوضةى ئاماذةثيَلساو بسيتيني هة مليى قوزيني جطة هة‬ ‫منوونةى ‪ C3‬كة بسيتية هة قوزِى ملني‪.‬‬

‫‪35‬‬

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