1 Portland cement and its major constituent phases 1

1.1 Introduction 1
1.1.1 Portland cement: general 1
1.1.2 Types of Portland cement 2
1.1.3 Cement chemical nomenclature and other abbreviations 3

1.2 Alite 4
1.2.1 Polymorphism and crystal structure 4
1.2.2 Tricalcium silicate solid solutions 7
1.2.3 Compositions of alites in clinkers 7
1.2.4 Polymorphic modifications of the alites in clinkers 9
1.2.5 X-ray powder patterns and densities of tricalcium silicate and alites 12
1.2.6 Optical, thermal and other data 13

1.3 Belite 13
1.3.1 Polymorphism and crystal structure 13
1.3.2 Polymorphic forms and textures in clinker belites 16
1.3.3 Compositions of belites in clinkers 18
1.3.4 Cell parameters, X-ray powder patterns and other data 18

1.4 Aluminate 19
1.4.1 Crystal structure: cubic, orthorhombic and monoclinic modifications 19
1.4.2 Other modifications 21
1.4.3 Structural modifications of clinker aluminates 22
1.4.4 Compositions of clinker aluminates 23
1.4.5 X-ray powder data, densities and optical properties 24

1.5 Ferrite 24
1.5.1 Crystal structure and composition in the
Ca2(AlJCFei_JC)2O5 series 24
1.5.2 Compositions of clinker ferrites 26
1.5.3 Crystal data and X-ray powder patterns for ferrites
containing substituent ions 27
1.5.4 Optical, magnetic and other data 28
2 High-temperature chemistry 29

2.1 Introduction 29

2.2 Systems containing CaO with SiO2 or A12O3 or both 29

2.2.1 The CaO-SiO2 system 29
2.2.2 The CaO-Al2O3 system 30
2.2.3 Ci2A7 and derived structures 31
2.2.4 C5A3, C2A and C4A3 33
2.2.5 The CaO-Al2O3-SiO2 system 33
2.2.6 Clinker formation in the CaO-Al2O3-SiO2 system 35

2.3 Systems containing Fe2O3 36

2.3.1 The CaO-Al2O3-Fe2O3 system 36
2.3.2 The CaO-Al2O3-Fe2O3-SiO2 system 38
2.3.3 Clinker formation in the CaO-Al2O3-Fe2O3-SiO2 system 40

2.4 Systems containing MgO or FeO 42

2.4.1 General 42
2.4.2 Effect of MgO on equilibria in the CaO-Al 2O3-Fe2O3-SiO2 system 43
2.4.3 Phases structurally related to gehlenite 45

2.5 Systems containing alkalis or SO3 or both 46

2.5.1 Phases 46
2.5.2 Equilibria 49

2.6 Systems with other components 50

2.6.1 Fluorides and fluorosilicates 50
2.6.2 Carbonates 52

2.7 Laboratory preparation of high-temperature phases 52

3 The chemistry of Portland cement manufacture 55
3.1 General considerations 55
3.1.1 Summary of the reactions in clinker formation 55
3.1.2 Lime saturation factor, silica ratio and alumina ratio 56
3.1.3 The Bogue calculation 57
3.1.4 Enthalpy changes in clinker formation 58

3.2 Raw materials and manufacturing processes 60

3.2.1 Raw materials and fuel 60
3.2.2 Dry and wet processes; energy requirements 61
3.2.3 The dry process; suspension preheaters and precalciners 61
3.2.4 The rotary kiln 63
3.2.5 Circulation of volatiles; dust; cooling of clinker 64
3.2.6 Other processes for clinker production; clinker grinding 64

Contents
3.3 Reactions below about 1300°C 65
3.3.1 Decomposition of carbonate minerals 65
3.3.2 Decomposition of clay minerals and formation of products 66
3.3.3 Sampling from cement kilns or preheater outlets 67
3.3.4 Reaction mechanisms 68
3.3.5 Condensation or reaction of volatiles 69

3.4 Reactions at 1300-1450°C 70

3.4.1 Quantity of liquid formed 70
3.4.2 Burnabilities of raw mixes 72
3.4.3 Nodulization 74
3.4.4 Formation and recrystallization of alite 74
3.4.5 Evaporation of volatiles; polymorphic transitions 75
3.4.6 Effects of reducing conditions; colour of clinker 76

3.5 Reactions during cooling, grinding or storage 11

3.5.1 Solidification of the clinker liquid: indications from pure systems 77
3.5.2 Do Portland cement clinkers contain glass or C12A7? 77
3.5.3 Evidence from X-ray microanalysis 79
3.5.4 Effects of cooling rate on the aluminate and ferrite phases 79
3.5.5 Other effects of cooling rate 80
3.5.6 Crystallization of the sulfate phases 81
3.5.7 Quantitative estimation of the distributions of alkalis and SO3 between phases 81
3.5.8 Changes during grinding or storage 84

3.6 Effects of minor components 84

3.6.1 General 84
3.6.2 Effects of s-block elements 85
3.6.3 Effects of p- and d-block elements 86
4 Properties of Portland clinker and cement 89
4.1 Macroscopic and surface properties 89
4.1.1 Unground clinker 89
4.1.2 Particle size distribution of ground clinker or cement 89
4.1.3 Specific surface area determination 91
4.1.4 Particle size distribution, phase composition and cement properties 92
4.1.5 Chemical analysis 93

4.2 Light microscopy 93

4.2.1 General 93
4.2.2 Effects of bulk composition, raw feed preparation and ash deposition 95
4.2.3 Effects of burning conditions and cooling rate 95
4.2.4 Applications of light microscopic investigations 96

4.3 Scanning electron microscopy, X-ray diffraction and other techniques 97

4.3.1 Scanning electron microscopy 97
4.3.2 X-ray diffraction 99
4.3.3 Chemical or physical methods for separation of phases 100
4.3.4 Other methods 102

4.4 Calculation of quantitative phase composition from bulk chemical analysis 102
4.4.1 General 102
4.4.2 Modified Bogue calculation 102
4.4.3 Mass balance calculations 104
4.4.4 Limitations and modifications of the modified Bogue calculation 104

4.5 Physical methods for determining quantitative phase composition 106

4.5.1 General 106
4.5.2 Light microscopy 106
4.5.3 Quantitative X-ray diffraction analysis (QXDA) 106
4.5.4 Comparison of results of different methods 108

4.6 Reactivities of clinker phases 109

4.6.1 Effect of major compositional variation 109
4.6.2 Effects of ionic substitutions, defects and variation in polymorph 110
4.6.3 Ferrite reactivity; effect of complexing in solution 112
5 Hydration of the calcium silicate phases 113
5.7 Introduction 113
5.1.1 Definitions and general points 113
5.1.2 Experimental considerations; carbonation 114
5.1.3 Calcium hydroxide 116

5.2 Composition, density and other data for C-S-H gel 118
5.2.1 Calcium hydroxide content, thermal analysis and indirect determination of the Ca/Si
ratio 118
5.2.2 Water content 119
5.2.3 Density and infrared spectra 121

5.3 Microstructure, microanalysis and electron diffraction 123

5.3.1 Microstructure 123
5.3.2 Stages in micro structural development 123
5.3.3 X-ray microanalysis 126
5.3.4 Analytical electron microscopy 127
5.3.5 Electron diffraction 128

5.4 More highly ordered phases related to C-S-H gel 128

5.4.1 General 128
5.4.2 l-4nm tobermorite 129
5.4.3 Jennite 131
5.4.4 C-S-H(I) 132
5.4.5 Products formed in suspensions from C3S C2S; C-S-H(II) 133

5.5 Silicate anion structure 134

5.5.1 Introduction 134
5.5.2 C-S-H gel of calcium silicate or cement pastes: chemical methods 135
5.5.3 C-S-H gel of calcium silicate or cement pastes: nuclear magnetic resonance 137
5.5.4 C-S-H(I) and other products made in suspension 138

5.6 The nanostructures of C-S-H gel and related materials 140

5.6.1 Broad features and tobermorite-based models for C-S-H(I) 140
5.6.2 Tobermorite-based models for the C-S-H of calcium silicate and cement pastes 141
5.6.3 A mixed tobermorite-jennite model for the C-S-H of calcium silicate and cement pastes
142
5.6.4 Other models for the C-S-H of calcium silicate and cement pastes 144

5.7 Equilibria 145

5.7.1 Solubility relations 145
5.7.2 Species in solution 147
5.7.3 Thermochemistry and thermodynamics 148
5.7.4 Effects of alkalis and of gypsum 149

5.8 Kinetics and mechanisms 150

5.8.1 C3S: experimental data 150
5.8.2 C3S: the initial reaction 153
5.8.3 C3S: the induction period 153
5.8.4 The main reaction (C3S and /?-C2S) 155
5.8.5 Early hydration of (3-C2S 156
6 Hydrated aluminate, ferrite and sulfate phases 157
6.1 AFm phases 157
6.1.1 Compositional and structural principles 157
6.1.2 The C4AHX, C4AC05Hx and C4ACHX phases 159
6.1.3 The C4ASHX phases 161
6.1.4 Other AFm phases containing aluminium 161
6.1.5 AFm phases containing iron 164
6.1.6 XRD patterns, thermal behaviour, optical properties and IR spectra 164

6.2 AFt phases 166

6.2.1 Compositions and crystal structures 166
6.2.2 Ettringite analogues and solid solutions 168
6.2.3 Properties 169

6.3 Other hydrated phases 170

6.3.1 Hydrogarnet phases 170
6.3.2 CAH10 171
6.3.3 Brucite, hydrotalcite and related phases 173
6.3.4 Sulfate phases 174

6.4 Equilibria and preparative methods 176

6.4.1 The CaSO4-H2O, CaSO4-Ca(OH)2-H2O and
CaSO4-K2SO4-H2O systems 176
6.4.2 The CaO-Al2O3-H2O and CaO-Al2O3-SO3-H2O systems 177
6.4.3 Systems including Na2O, K2O, SiO2, CaCO3 or CaCl2 180
6.4.4 Preparative methods 181

6.5 Hydration reactions of the aluminate and ferrite phases 182

6.5.1 Reaction of C3A with water or with water and
calcium hydroxide 182
6.5.2 Reaction of C3A with water in the presence of
calcium sulfate 182
6.5.3 Effects of temperature, alkali, tricalcium silicate and CO2 184
6.5.4 Reaction of the ferrite phase 184
6.5.5 Enthalpy changes 186
7 Hydration of Portland cement 187
7.1 Evidence from X-ray diffraction, thermal analysis and infrared spectroscopy 187
7.1.1 Introduction; formation of calcium hydroxide and C-S-H 187
7.1.2 Formation of hydrated aluminate or sulfoaluminate phases 188
7.1.3 Evidence from differential thermal analysis and infrared spectroscopy 189

7.2 Micro structure 191

7.2.1 Evidence from light and electron microscopy 191
7.2.2 The early period of hydration 193
7.2.3 The middle period of hydration 195
7.2.4 The late period of hydration 196

73 Analytical data for cement pastes 197

7.3.1 Unreacted clinker phases 197
7.3.2 Non-evaporable and bound water 197
7.3.3 Thermogravimetry and calcium hydroxide content 199
7.3.4 Hydrated aluminate and silicate phases 201
7.3.5 Analyses of individual phases 201
7.3.6 Silicate anion structure 204

7.4 Interpretation of analytical data 205

7.4.1 Substitution or admixed phases? 205
7.4.2 Fe2O3 in cement hydration products 207
7.4.3 MgO, SO3 and alkalis in cement hydration products 208
7.4.4 The stoichiometry of cement hydration 209

7.5 Calorimetry, pore solutions and energetics 212

7.5.1 The early and middle periods 212
7.5.2 Pore solutions after the first day 214
7.5.3 Energetics of cement hydration 215

7.6 Actions of calcium sulfate and of alkalis 218

7.6.1 Setting 218
7.6.2 Optimum gypsum 219
7.6.3 Effects of alkalis 221

7.7 Kinetics and modelling of the hydration process 222

7.7.1 Experimental data 222
7.7.2 Interpretation of kinetic data 224
8 Structure and properties of fresh and hardened Portland cement pastes 227
8.1 Fresh pastes 227
8.1.1 Workability 227
8.1.2 Rheology; viscometry 227
8.1.3 Oscillatory and controlled-stress rheometry 229
8.1.4 Models of fresh paste structure 230

8.2 Hardened cement pastes; models of structure 231

8.2.1 The Powers-Brownyard model 231
8.2.2 Minimum water/cement ratio for complete hydration; chemical shrinkage 232
8.2.3 Calculation of volumetric quantities 234
8.2.4 Later models of cement gel structure 235

8.3 Mathematical modelling of micro structure and properties 237

8.3.1 Introduction 237
8.3.2 Calculation of porosities and of volume fractions of solid phases 238
8.3.3 Microstructural models 242

8.4 Experimental methods for studying pore structure 243

8.4.1 General points 243
8.4.2 Determination of porosities by pyknometry 243
8.4.3 Sorption isotherms; specific surface areas 244
8.4.4 Pore size distributions 246
8.4.5 Mercury intrusion porosimetry (MIP) 247
8.4.6 Scanning electron microscopy 249
8.4.7 AC impedance spectroscopy 249
8.4.8 Other methods 251

8.5 Strength 252

8.5.1 Empirical relations between compressive strength and porosity 252
8.5.2 Relations between strength and microstructure or pore size distribution 253
8.5.3 Mechanisms of failure 255

8.6 Deformation 255

8.6.1 Modulus of elasticity 255
8.6.2 Creep and shrinkage 256

8.7 Permeability and diffusion 258

8.7.1 Permeability to water 258
8.7.2 Diffusion of ions and gases 259
9 Composite cements 261
9.1 Introduction 261

9.2 Blastfurnace slag 262

9.2.1 Formation, treatment and use in composite cements 262
9.2.2 Factors affecting suitability for use in a composite cement 263
9.2.3 X-ray diffraction and microstructure of slags 264
9.2.4 Internal structures of slag glasses 265
9.2.5 Hydration chemistry of slag cements 266
9.2.6 X-ray microanalysis 267
9.2.7 Stoichiometry of slag cement hydration 270
9.2.8 Activation of slag glasses 271
9.2.9 Alkali-activated slag cements 271
9.2.10 Supersulfated cements 272

9.3 Flyash (pulverized fuel ash) low in CaO 272

9.3.1 Properties 272
9.3.2 Factors governing suitability for use in composite cements 274
9.3.3 Rates of consumption of clinker phases and flyash, and contents of calcium hydroxide
275
9.3.4 Microstructure and compositions of the hydration products 277
9.3.5 Stoichiometry of flyash cement hydration 279
9.3.6 The nature of the pozzolanic reaction 280

9.4 Natural pozzolanas 280

9.4.1 Properties 280
9.4.2 Hydration reactions 281

9.5 Silica fume (condensed silica fume, microsilica) 284

9.5.1 Properties 284
9.5.2 Hydration reactions 285

9.6 Other mineral additions 286

9.6.1 Class Cflyash 286
9.6.2 Other pozzolanic or hydraulic additions 288
9.6.3 Calcium carbonate and other mineral additions 289

9.7 Pore structures and their relation to physical properties 290

9.7.1 Calculated porosities for pastes containing slag or flyash 290
9.7.2 Modelling of pore structure 290
9.7.3 Experimental determination of porosities and pore size distributions 291
9.7.4 Relations between pore structure and physical properties 293
10 Calcium aluminate, expansive and other cements 295
10.1 Calcium aluminate cements 295
10.1.1 Introduction 295
10.1.2 Manufacture; chemical and mineralogical compositions 295
10.1.3 Reactivities of the phases and methods of studying hydration 298
10.1.4 Hydration reactions and products 298
10.1.5 Thermodynamic calculations 301
10.1.6 Setting times; mixing and placing 303
10.1.7 Microstructural development 304
10.1.8 Hardening; effects of conversion 306
10.1.9 Chemical admixtures 309
10.1.10 Mixtures with calcite, slag, gypsum or Portland cement 310
10.1.11 Reactions of calcium aluminate cement concrete with external agents 311
10.1.12 Refractory castables 312

10.2 Expansive cements 313

10.2.1 General 313
10.2.2 Types of expansive cement 314
10.2.3 Mechanism of expansion in Type K cements 315

10.3 Other cements 317

10.3.1 Very rapidly hardening cements 317
10.3.2 Energy reduction in the manufacture of cements 319
10.3.3 Reactive belites 320
10.3.4 Cements containing belite and a highly reactive constituent 321
10.3.5 Alinite cements 321
11 Admixtures and special uses of cements 323
11.1 Introduction 323

11.2 Organic retarders and accelerators 323

11.2.1 Retarders 323

11.2.2 Mechanism of retardation 324
11.2.3 Practical retarders 327
11.2.4 Organic accelerators 328

11.3 Air-entraining agents and grinding aids 328

11.3.1 Air-entraining agents 328
11.3.2 Grinding aids 329

11.4 Water reducers and super'plasticizers 330

11.4.1 Water reducers 330
11.4.2 Superplasticizers 330
11.4.3 Mode of action of water reducers and superplasticizers 332
11.4.4 Zeta potential, rheology and nature of the sorbent phases 333
11.4.5 Reasons for the enhanced dispersing power of superplasticizers 334

11.5 Inorganic accelerators and retarders 334

11.5.1 Accelerators of setting and hardening 334
11.5.2 Mode of action 335
11.5.3 Effects on the composition and structure of the hydration products 337
11.5.4 Precipitation effects; inorganic retarders and setting accelerators 338

11.6 Effects of high or low temperatures at atmospheric pressure 339

11.6.1 Hydration at 25-100°C 339
11.6.2 Effects on kinetics, ultimate extent of hydration and microstructure 339
11.6.3 Low temperatures 341

11.7 High-pressure steam curing 341

11.7.1 General 341
11.7.2 Basic chemistry of autoclave processes 342
11.7.3 Mechanisms of reaction and equilibria 344
11.7.4 Characteristics of hydrothermally formed C-S-H and tobermorite 344

11.8 Oil well cementing 346

11.8.1 General 346
11.8.2 Types of cement and of admixture 346
11.8.3 Effects of temperature and pressure 348

11.9 Very high strength cement-based materials 348

11.9.1 General 348
11.9.2 DSP concretes 349
11.9.3 MDF cements 349