CaO–SiO2–Al2O3–Fe Oxides Chemical System , livre ebook

352

pages

English

Ebooks

2021

Écrit par
François Sorrentino , Denis Damidot , Charles Fentiman

Publié par
EDP Sciences

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352

pages

English

Ebooks

2021

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Obtenez un accès à la bibliothèque pour le consulter en ligne En savoir plus

Publié par

EDP Sciences

Date de parution

08 février 2021

Nombre de lectures

EAN13

9782759825363

Langue

English

Poids de l'ouvrage

19 Mo

This book describes and comments on the results of research devoted to the studies of phase assemblages in the CaO-SiO2-Al2O3-Fe oxides chemical system, their stability and their evolution in our environment (temperature, pressure). Its aim is to be a research support, not only for researchers and development engineers but also more generally for others interested in materials sciences.

The book is divided in two parts; the first devoted to a description of ‘the system’ using phase diagrams. The second explores the properties and uses of some of the minerals that are in widespread industrial and commercial use.

Much of the work presented in this book is fully original and corresponds to the research undertaken by François Sorrentino from his time at the chemistry department of the University of Aberdeen during the early 1970’s, to recent years when he has resumed his interest in mineral research, particularly related to the synthesis of calcium silicates and calcium aluminates, and their industrial manufacture.

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . III

Part I - Descriptions

CHAPTER 1

One-Component Chemical Systems: CaO, SiO2, Al2O3 and Fe Oxides . . . . . . 3

1.1 CaO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

1.1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

1.1.2 Mineralogy, Structure and Stability . . . . . . . . . . . . . . . . . . . . . 3

1.1.3 Properties and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

1.2 SiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1.2.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1.2.3 Structure and Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

1.2.4 Properties and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

1.3 Al2O3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

1.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

1.3.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1.3.3 Structure and Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1.3.4 Properties and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

1.4 Fe Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1.4.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1.4.3 Structure and Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1.4.4 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

1.4.5 Properties and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

CHAPTER 2

Binary Chemical Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.1 CaO–SiO2 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.1.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.1.3 Structure, Polymorphism and Solid Solution . . . . . . . . . . . . . . . 18

2.1.4 Stability and Phase Diagram of CaO–SiO2 System . . . . . . . . . . 25

2.1.5 Synthesis of Calcium Silicates . . . . . . . . . . . . . . . . . . . . . . . . . . 27

2.2 Al2O3–SiO2 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

2.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

2.2.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

2.2.3 Structure, Polymorphism and Solid Solutions . . . . . . . . . . . . . . 33

2.2.4 Stability and Phase Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . 37

2.2.5 Synthesis of Alumino-Silicates . . . . . . . . . . . . . . . . . . . . . . . . . 41

2.3 Al2O3–Fe Oxides System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

2.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

2.3.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

2.3.3 Structure, Polymorphism and Solid Solution . . . . . . . . . . . . . . . 44

2.3.4 Stability and Phase Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . 45

2.3.5 Synthesis of Iron Aluminates . . . . . . . . . . . . . . . . . . . . . . . . . . 48

2.4 CaO–Al2O3 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

2.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

2.4.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

2.4.3 Structure, Polymorphism and Solid Solution . . . . . . . . . . . . . . . 49

2.4.4 Stability and Phase Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . 55

2.4.5 Synthesis of Calcium Aluminates . . . . . . . . . . . . . . . . . . . . . . . 57

2.5 SiO2–Fe Oxides System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

2.5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

2.5.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

2.5.3 Structure, Polymorphism and Solid Solution . . . . . . . . . . . . . . . 63

2.5.4 Liquid FeO–Fe2O3–SiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

2.5.5 Stability and Phase Diagram of the FeO–Fe2O3–SiO2 System . . . . 67

2.5.6 Synthesis of Iron Silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

2.6 CaO–Fe Oxides System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

2.6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

2.6.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

2.6.3 Structure, Polymorphism and Solid-Solutions . . . . . . . . . . . . . . 72

2.6.4 Stability and Phase Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . 75

2.6.5 Synthesis of Calcium Ferrite . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

CHAPTER 3

Ternary Chemical Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

3.1 General Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

3.2 CaO–Al2O3–SiO2 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

3.2.1 Ternary Constituents of the CaO–Al2O3–SiO2 System . . . . . . . 83

3.2.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

3.2.3 Structure and Solid Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . 85

3.2.4 Stability and Phases Diagrams (At One Atmosphere) . . . . . . . . 90

3.2.5 Compounds Obtained in Special Conditions . . . . . . . . . . . . . . . 97

3.2.6 Stability Relative to Temperature or Pressure and Both . . . . . . 98

VIII Contents

3.2.7 Thermodynamic Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99

3.2.8 Synthesis of Calcium Silicoaluminate . . . . . . . . . . . . . . . . . . . . 101

3.3 Al2O3–SiO2–Fe Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103

3.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103

3.3.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103

3.3.3 Structure and Solid Solution. . . . . . . . . . . . . . . . . . . . . . . . . . . 103

3.3.4 Stability and Phase Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . 104

3.3.5 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

3.4 CaO–SiO2–Fe Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

3.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

3.4.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

3.4.3 Structure and Solid Solution. . . . . . . . . . . . . . . . . . . . . . . . . . . 110

3.4.4 Stability and Phase Diagrams in Air. . . . . . . . . . . . . . . . . . . . . 112

3.4.5 Stablity and Phase Diagram in the CaO–SiO2–FeO System . . . . 117

3.4.6 CaO–SiO2–FeOx System at Various Oxygen Pressures . . . . . . . 126

3.4.7 Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

3.4.8 Preparation and Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132

3.5 CaO–Al2O3–Fe Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

3.5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

3.5.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

3.5.3 Structure and Solid Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . 135

3.5.4 Stability and Phase Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . 140

3.5.5 Liquidus in Reducing Atmosphere . . . . . . . . . . . . . . . . . . . . . . 143

3.5.6 Model of the System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145

3.5.7 Formation and Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145

CHAPTER 4

Quaternary Chemical Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147

4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147

4.1.1 Principle of Phase Equilibrium in a Quaternary System . . . . . . 147

4.2 CaO–SiO2–Al2O3–Fe2O3 System in Air . . . . . . . . . . . . . . . . . . . . . . . . 152

4.2.1 Quaternary Constituents of the CaO–SiO2–Al2O3–Fe

Oxides System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

4.2.2 Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

4.2.3 Mineralogy Structure Stability . . . . . . . . . . . . . . . . . . . . . . . . . 158

4.2.4 Formation and Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173

4.3 CaO–Al2O3–SiO2–FeO System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173

4.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173

4.3.2 Ternary Systems Located Within the CaO, Al2O3, SiO2,

FeO Tetrahedron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173

4.3.3 Binary Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181

4.3.4 Crystallized Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182

4.3.5 Univariant Lines and Quaternary Invariant Points . . . . . . . . . . 182

4.3.6 2CaO·SiO2–CaO·SiO2–Gehlenite–FeO Quaternary System . . . . 183

Contents IX

CHAPTER 5

Quinary Chemical Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189

5.1 Introduction – Presentation of Quinary Data . . . . . . . . . . . . . . . . . . . 189

5.2 CaO–SiO2–Al2O3–FeO–Fe2O3 System . . . . . . . . . . . . . . . . . . . . . . . . . 189

5.2.1 Stability and Phase Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . 189

5.2.2 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192

References of Part I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193

Part II - Applications

CHAPTER 6

Applications to Hydraulic Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211

6.1 General Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211

6.2 Portland Cements (PC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212

6.2.1 Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212

6.2.2 PC Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220

6.2.3 Conclusions – Prediction of the Properties . . . . . . . . . . . . . . . . 226

6.3 Calcium Aluminate Cements (CAC) . . . . . . . . . . . . . . . . . . . . . . . . . . 227

6.3.1 CAC Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227

6.3.2 CAC Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234

6.4 Special Cements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237

6.4.1 Fast-Setting Cements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237

6.4.2 Geopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243

6.4.3 Oil Well Cements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246

6.4.4 Expansive Cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251

6.4.5 Dental Cements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253

6.4.6 Glass Cements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259

CHAPTER 7

Application to Metal Refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

7.1 General Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

7.2 Slags from Iron and Steel Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

7.2.1 Blast Furnace Slags (BFS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

7.2.2 Converter Slags (Basic Oxygen Process or LD processing) . . . . 266

7.2.3 EAF Slags: High Carbon Steel . . . . . . . . . . . . . . . . . . . . . . . . . 269

7.2.4 Ladle Slag (Secondary Metallurgy) – Stainless – High Alloy

Steel Production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269

7.2.5 Refining Under Reducing Slag . . . . . . . . . . . . . . . . . . . . . . . . . 270

7.3 Formation and Properties of Liquid Slags . . . . . . . . . . . . . . . . . . . . . . 271

7.4 Slags from Non Ferrous Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272

7.4.1 Copper Slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272

7.4.2 Silico-Manganese Slag. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272

X Contents

CHAPTER 8

Application to Refractory Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

8.2 Raw Materials Based on Al2O3 and SiO2. . . . . . . . . . . . . . . . . . . . . . . 276

8.2.1 Natural Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276

8.2.2 Synthetic Raw Material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277

8.3 Applying Refractory Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278

8.3.1 Brick and Monolithic Refractories . . . . . . . . . . . . . . . . . . . . . . . 278

8.3.2 Refractory Cement and Mortar . . . . . . . . . . . . . . . . . . . . . . . . 281

8.4 Refractories Consuming Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286

8.4.1 Iron and Steel Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286

8.4.2 Non-Ferrous Metal Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . 287

8.4.3 Cement Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287

8.4.4 Whiteware, Traditional Ceramic Industry . . . . . . . . . . . . . . . . . 288

8.4.5 High-Tech Ceramic Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . 288

8.4.6 Glass Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288

CHAPTER 9

Application of the Glassy Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291

9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291

9.2 Structure of Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292

9.3 Classification of Glass Products Containing CaO, Al2O3, SiO2

and Fe Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293

9.4 Products, Chemistry and Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294

9.4.1 High Silica Glass – Vycor Glass . . . . . . . . . . . . . . . . . . . . . . . . 294

9.4.2 Soda-Lime Glass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295

9.4.3 Sodium Borosilicate – Glass Fibres . . . . . . . . . . . . . . . . . . . . . . 295

9.4.4 Aluminosilicate Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297

9.4.5 Special Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299

CHAPTER 10

Application of Ceramic Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303

10.1 Introduction to Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303

10.2 Structure of Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303

10.2.1 Processing of Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . 303

10.2.2 Shaping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304

10.2.3 Physico-Chemical Changes During Firing . . . . . . . . . . . . . . . 305

10.3 Classification of Ceramic Products Containing CaO, SiO2,

Al2O3 and Fe Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305

10.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305

10.3.2 Traditional Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305

10.3.3 Ceramics in the Construction Sector Ceramics . . . . . . . . . . . 312

10.3.4 High Technology Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . 313

Contents XI

CHAPTER 11

Application as Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315

11.1 General Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315

11.2 Mono-Component . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317

11.2.1 Calcium Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317

11.2.2 SiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318

11.2.3 Alumina . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319

11.2.4 Fe oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320

11.3 Multi-Components By-Products from Industrial Process . . . . . . . . . . 321

11.3.1 Slags . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321

11.3.2 Fly Ashes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324

11.3.3 Red Mud (KUR 1997) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326

11.3.4 Cement Kiln Dust (CKD) . . . . . . . . . . . . . . . . . . . . . . . . . . 327

11.4 Multi-Components from Natural Origin . . . . . . . . . . . . . . . . . . . . . . 328

11.4.1 Natural Pozzolans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328

11.4.2 Metakaolin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330

11.4.3 Rice Husk Ashes (RHA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331

11.4.4 Wollastonite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332

References of Part II. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

Voir

Publié par

EDP Sciences

Date de parution

08 février 2021

EAN13

9782759825363

Langue

English

Poids de l'ouvrage

19 Mo

Materials

François SORRENTINO, Denis DAMIDOT and Charles FENTIMAN

CHEMICAL SYSTEMS

CaO–SiO –Al O –Fe Oxides 2 2 3 Chemical System Description and Applications

CHEMICAL SYSTEMS

ISBN : 978-2-7598-2480-9

CaO–SiO –Al O –Fe Oxides 2 2 3 Chemical System Description and Applications

Materials

François SORRENTINO, Denis DAMIDOT and Charles FENTIMAN

This book describes and comments on the results of research devoted to the studies of phase assemblages in the CaO-SiO -Al O -Fe oxides 2 2 3 chemical system, their stability and their evolution in our environment (temperature, pressure). Its aim is to be a research support, not only for researchers and development engineers but also more generally for others interested in materials sciences.

Dr. François SORRENTINO worked as project manager and senior scientist at the Lafarge research laboratories, and also as Research Director of CNRS.

Prof. Denis DAMIDOT is Professor at Institut Mines-Télécom Lille Douai where his research is devoted to cementitious materials through a mainly physico-chemical approach based on experiments and numerical simulation.

Dr.Charles FENTIMAN works as a materials consultant and is organiser of international conferences about Calcium Aluminate Cements.

www.edpsciences.org

Materials

François SORRENTINO, Denis DAMIDOT and Charles FENTIMAN

CaO–SiO2–Al2O3–Fe Oxides Chemical System

Description and Applications

Printed in France

EDP Sciences–ISBN(print): 9782759824809–ISBN(ebook): 9782759825363 DOI: 10.1051/9782759824809

All rights relative to translation, adaptation and reproduction by any means whatsoever are reserved, worldwide. In accordance with the terms of paragraphs 2 and 3 of Article 41 of the French Act dated March 11, 1957,“copies or reproductions reserved strictly for private use and not intended for collective use”and, on the other hand, analyses and short quotations for example or illustrative purposes, are allowed. Otherwise,“any representation or reproduction–whether in full or in part–without the consent of the author or of his successors or assigns, is unlawful”(Article 40, paragraph 1). Any representation or reproduction, by any means whatsoever, will therefore be deemed an infringement of copyright punishable under Articles 425 and following of the French Penal Code.

Science Press, EDP Sciences,2021

Preface

Aim of the Book

This book describes and comments on the results of research devoted to the studies of phase assemblages in the CaO–SiO2–Al2O3–Fe oxides chemical system (men tioned‘the system’thereafter), their stability and their evolution in our environ ment (temperature, pressure). Its aim is to be a research support, not only for researchers and development engineers but also more generally for others interested in materials sciences. Indeed; it concerns oxygen, silicon, aluminium, calcium and iron that are by mass the most abundant elements in the earth crust and the most widely used by human beings. Thus, not only does this show the diversity of the properties of the combinations of these elements, but also reflects the abundance as a primary reason for the diversity of their uses. Consequently, the book is divided into two parts; the first one is devoted to a description of‘the system’using phase diagrams and the second one presents the properties of some of the constituents that are in widespread industrial and com mercial use. Much of the work reported in this book is fully original, as it reports records of the research that Dr François Sorrentino undertook in the chemistry department of Aberdeen University in the early seventies and then the research he carried out as manager ofMineral Research Processing Companydevoted to the synthesis of minerals. The laboratory synthesis of calcium silicates and calcium aluminates, and their indus trial manufacture were the main interests of the development of this Company.

Summary of Part I–Description of the CaO–SiO2–Al2O3–Fe Oxides Chemical System

The first part is an exhaustive literature survey of‘the system’. References are quoted using the first three letters of the name of the first author followed by the year of publication. For example, ARA 1959 corresponds to Aramaki S. and Roy R.

DOI: 10.1051/9782759825219.c901 Science Press, EDP Sciences, 2020

Preface

(1959) Revised equilibrium diagram for the system Al2O3–SiO2,Nature184, 631. The major data relevant to this system and their combinations, useful for their applications in the daily lives of human being have been collected. Entirely recon structed, revisited and redrawn phase diagrams are then described from the col lected data, and experimental data from personal experience added. When data overlap or interfere, the author takes the responsibility of the choices that were made. In each chapter, the constituents are identified by their formula in the intro duction. A list of the most probable existing constituents is given and written both as chemical formula (e.g.Ca3SiO5) and oxidesbased formula (e.g.3CaOSiO2). Common/historical names are also given when known, for instance when named after a locality such as the mineral, Andalusite (named after Andalusia), or when named after a person, typically the discovering geologist or chemist, for instance Wollastonite, named after William Hyde Wollaston (1766–1828). Then, the subchapter, entitled mineralogy, gives the mineralogical composition, the location and the mechanism of its formation. The main crystallographic characteristics and the polymorphic forms are then described in the subchapter related to crystallog raphy. Solid solutions are only treated in the context of‘the system’that is narrower than the global chemical system. The stability of the phase assemblages depending on temperature and pressure is then reported in the subchapter dealing with phase diagrams. The experimental phase diagrams are redrawn from sets of experimental data found in the literature. Moreover, thermodynamic models have been used to calculate the phase diagram and compare it to its experimental counterpart. Finally, the last subchapter provides methods to synthesize the constituents that have been described thanks to the knowledge of their conditions of formation gained from phase diagrams.

Summary of Part II–Applications of the CaO–SiO2–Al2O3–Fe Oxides Chemical System Part II describes the main applications of the oxides within‘the system’(except for the primary oxides where applications are reported in part I). It is hardly surprising to find that there is a large diversity of applications found with minerals and sub stances containing these elements. The most common combinations are oxides (silicon, aluminium, iron), or nonoxide minerals such as carbonates or sulphides. Other combinations between these elements allow us to extend the fields of appli cations of the phase relations known in the simpler system. The work presented in this part, is not only a bibliography synthesis, although the data come, in a large part from the literature, but they have been enriched by personal experience, in the field of hydraulic binders, refractory glass and ceramics that are part of Dr François Sorrentino’s professional career. The applications are divided into three levels of applications, the last one being the closest to the enduser or the customer (tableP.1). The first level describes the application of the CaO–SiO–Al O–Fe oxides chemical system with a minimum of 2 2 3

Preface

TAB. P.1–Examples of the three levels of applications of the CaO–Al2O3–SiO2–Fe oxides system. Starting First level Second level Third level (end use) material CaO Agriculture Slag forming, cement Civil engineering (buildings) SiO2engineering (cladding materialcement Civil Aggregates Glass, for buildings), cooking ware, container Al2O3(Al), gems, Refractory Aluminium Vessel, kiln lining, building, aircraft glass (with Ge), devices, wave guide abrasive Fe Pigments Steel, slags Car industry, steel bar, military oxides devices

treatment such as crushing or grinding. For example, the use of Fe2O3as a pigment, the use of CaO in agriculture or silica as quartz for aggregates. The second level concerns the use of‘the system’as a precursor for the synthesis of other materials such as the manufacture of steel by reduction of Fe2O3or the combination of CaO, silica, alumina and iron oxides to manufacture cement. The third level represents the end level for which the application is close to the enduser or to the customer. The fields of applications in‘the system’reported in part II are construction, metallurgy, glass and ceramics but also specific uses such as refractory materials and fillers.

Acknowledgement

I would like to thank Prof. Denis Damidot and Dr Charles Fentiman for taking part in the process of writing and editing this book. I also would like to thank my wife Dr Danielle Sorrentino for her unconditional support.

Dr François Sorrentino

Contents

Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Part I  Descriptions

CHAPTER 1 OneComponent Chemical Systems: CaO, SiO2, Al2O3and Fe Oxides. . . . . . 1.1 CaO. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1.2 Mineralogy, Structure and Stability. . . . . . . . . . . . . . . . . . . . . 1.1.3 Properties and Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 SiO2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.3 Structure and Stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.4 Properties and Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3 Al2O3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3.3 Structure and Stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3.4 Properties and Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4 Fe Oxides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4.3 Structure and Stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4.4 Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4.5 Properties and Applications. . . . . . . . . . . . . . . . . . . . . . . . . . .

CHAPTER 2 Binary Chemical Systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 CaO–SiO2System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

III

3 3 3 3 4 5 5 5 6 6 7 7 8 8 9 10 10 11 11 14 14

17 17 17 17

VIII

2.2

2.3

2.4

2.5

2.6

Contents

2.1.3 Structure, Polymorphism and Solid Solution. . . . . . . . . . . . . . . 2.1.4 Stability and Phase Diagram of CaO–SiO2System. . . . . . . . . . 2.1.5 Synthesis of Calcium Silicates. . . . . . . . . . . . . . . . . . . . . . . . . . Al2O3–SiO2System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3 Structure, Polymorphism and Solid Solutions. . . . . . . . . . . . . . 2.2.4 Stability and Phase Diagram. . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.5 Synthesis of AluminoSilicates. . . . . . . . . . . . . . . . . . . . . . . . . Al2O3–Fe Oxides System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.3 Structure, Polymorphism and Solid Solution. . . . . . . . . . . . . . . 2.3.4 Stability and Phase Diagram. . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.5 Synthesis of Iron Aluminates. . . . . . . . . . . . . . . . . . . . . . . . . . CaO–Al2O3System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.3 Structure, Polymorphism and Solid Solution. . . . . . . . . . . . . . . 2.4.4 Stability and Phase Diagram. . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.5 Synthesis of Calcium Aluminates. . . . . . . . . . . . . . . . . . . . . . . SiO2–Fe Oxides System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.3 Structure, Polymorphism and Solid Solution. . . . . . . . . . . . . . . 2.5.4 Liquid FeO–Fe2O3–SiO2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.5 Stability and Phase Diagram of the FeO–Fe2O3–SiO2System. . . . 2.5.6 Synthesis of Iron Silicates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . CaO–Fe Oxides System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.3 Structure, Polymorphism and SolidSolutions. . . . . . . . . . . . . . 2.6.4 Stability and Phase Diagram. . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.5 Synthesis of Calcium Ferrite. . . . . . . . . . . . . . . . . . . . . . . . . . .

CHAPTER 3 Ternary Chemical Systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 General Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 CaO–Al O–SiO System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 3 2 3.2.1 Ternary Constituents of the CaO–Al2O3–SiO2System. . . . . . . 3.2.2 Mineralogy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.3 Structure and Solid Solutions. . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.4 Stability and Phases Diagrams (At One Atmosphere). . . . . . . . 3.2.5 Compounds Obtained in Special Conditions. . . . . . . . . . . . . . . 3.2.6 Stability Relative to Temperature or Pressure and Both. . . . . .

18 25 27 33 33 33 33 37 41 44 44 44 44 45 48 48 48 49 49 55 57 62 62 62 63 66 67 71 72 72 72 72 75 81

83 83 83 83 84 85 90 97 98

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