《The Chemistry of PORTLAND CEMENT SECOND EDITION 1995》

Ⅰ.The Chemistry of Clinker Formation1

1.HISTORY OF THE CEMENT INDUSTRY3

Cements in antiquity3

The Invention of Portland cement5

John Smeaton6

Byran Higgins7

Bergmann8

Joseph Parker8

L.J.Vicat9

J.F.John9

James Frost10

Joseph Aspdin10

I.C.Johnson11

The development of the cement industry12

David Saylor13

Growth of the industry14

Select bibliography20

2.CLASSIFICATION OF CEMENTS23

3.THE MANUFACTURE OF PORTLAND CEMENT37

Outline of operations37

Source of raw materials38

Proportioning of raw materials40

Preparation of kiln feed42

The Dry Process43

The Wet Process43

Flotation47

The burning operation51

American practice51

European innovations53

Treatment of clinker56

Properties of cement59

Combined processes in cement manufacture60

4.EARLY EXPERIMENTATION ON THE CONSTITUTION OF PORTLAND CEMENT63

The period of speculation63

Introduction of the scientific method65

Microscopic studies67

Henri Le Chatelier67

A.E.Tornebohm68

Comparison of researchers68

Other theories of the period70

Hypotheses of solid solution72

Clifford Richardson72

Wilhelm Micha？lis74

E.D.Campbell and A.H.White76

Constitutional formulas of cement compounds77

W.Asch and D.Asch77

Ernest Martin79

F.W.Clarke81

5.METHODS OF INVESTIGATION85

Petrographic technique85

Powder mounts and thin sections85

Polished sections86

Etching technique87

X-ray powder diffraction90

Electron microscopy and diffraction95

Chemical methods98

Free CaO98

Ca(OH)2 in set cement102

Free CaO and Ca(OH)2 in cement103

Determination of uncombined magnesia104

Spectrographic analysis106

Flame photometry108

Polarographic analysis109

Heat of solution110

Procedure110

Estimation of glass content113

6.HEAT TREATMENT IN MANUFACTURE121

The burning process121

Volatilization of alkalies126

Thermal reactions of clinker formation129

The cooling process139

7.THE PRINCIPAL CONSTITUENTS OF CLINKER145

Microscopic structure145

Tricalcium silicate148

Stability of 3CaO·SiO2148

The alite problem152

Dicalcium silicate160

Theα-βinversion160

α-C2S solid solution163

Theβ-γinversion170

Free CaO and MgO171

Interstitial material174

Rectangular dark interstitial material174

Prismatic interstitial material176

Amorphous dark interstitial material182

Light interstitial material184

Crystal structure187

Tricalcium aluminate188

Brownmiller’s metastable phase188

Dicalcium silicate191

Tricalcium silicate195

8.THE COMBINATION OF THE CEMENT COMPONENTS203

Reactions in the solid state203

Effects of particle size206

The effects of composition208

Temperature of liquid formation209

The amount of liquid formed215

The addition of mineralizers217

Effect of compound saturation218

9.DESIGN AND CONTROL OF CEMENT COMPOSITION225

Development of proportioning formulas225

The principle of chemical control235

Comparison of clinker compositions obtained by different methods238

10.CALCULATION OF PHASE COMPOSITION245

Equilibrium crystallization245

Equilibrium mixture containing liquid249

Classification of systems250

Nonequilibrium cooling255

Classification of crystallization areas255

Independent crystallization of liquid257

General equations263

Ⅱ.The Equilibria of Clinker Components269

11.THE PRINCIPLES OF HIGH-TEMPERATURE PHASE RESEARCH271

The phase rule271

Usefulness of the phase rule271

Derivation of the phase rule272

Binary systems274

Polycomponent systems279

No compound formation280

The course of crystallization281

Dahl’s method of computing composition282

Compound formation,stable at melting point284

Compound formation,unstable at melting point285

Stages followed with heat input287

Crystallization in ternary systems containing solid solutions289

Analytical treatment of multicomponent systems293

12.THE TECHNIQUES OF HIGH-TEMPERATURE PHASE RESEARCH299

General procedures299

Preliminary operations299

The quenching method300

The annealing method300

Differential thermal analysis302

Fnrnace equipment302

Electric muffle302

Containers for charges304

Quenching furnace305

Centrifuge furnace306

Platinum strip furnace308

Iridium furnace308

Iridium button furnace309

Resistance furnace309

Solar furnace310

Induction furnace310

Temperature control311

Calibration of thermocouples312

Equipment for differential thermal analysis313

Pilot plant319

13.THE SYSTEM CaO-Al2O3-SiO2323

The oxides323

Calcium oxide(lime,CaO)323

Silicon dioxide(silica,SiO2)324

Aluminum oxide(alumina,Al2O3)324

The system CaO-SiO2325

Phase relations325

Optical properties of the calcium silicates329

Preparation of the calcium silicates331

The system CaO-Al2O3334

Phase relations334

Composition of the calcium aluminates335

Optical properties of the calcium aluminates337

Preparation of the calcium aluminates338

The system Al2O3-SiO2339

The system CaO-Al2O3-SiO2339

Stability fields339

Crystallization areas344

Course of crystallization346

The field of portland cement349

14.SYSTEM CONTAINING MgO WITH CaO,Al2O3,SiO2355

MgO355

CaO-MgO355

MgO-Al2O3355

MgO-SiO2355

CaO-MgO-Al2O3356

CaO-MgO-SiO2357

C2S-MgO-C5A3358

CaO-MgO-Al2O3-SiO2360

15.SYSTEMS CONTAINING FeO,TiO2 AND P2O5365

The ferrous-oxide systems365

Fe3O4-Fe2O3365

CaO-FeO366

SiO2-FeO367

CaO-FeO-SiO2368

MgO-FeO-SiO2369

FeO-Al2O3-SiO2369

CaO-FeO-Al2O3-SiO2370

The titania systems371

TiO2371

TiO2-SiO2371

TiO2-Al2O3371

Na2O-TiO2372

CaO-TiO2-SiO2373

Systems containing P2O5373

16.SYSTEMS CONTAINING Fe2O3 WITH CaO AND SiO2377

Fe2O3377

CaO-Fe2O3377

CaO-C2S-CF378

CaO-C2S-C2F379

CaO-Fe2O3-CaCl2382

17.SYSTEMS CONTAINING MgO AND Fe2O3 WITH CaO AND Al2O3385

Al2O3-Fe2O3385

MgO-Fe2O3385

CaO-C5A3-CF385

C4AF-MgO390

CaO-CA-C4AF391

CaO-C5A3-C2F394

18.SYSTEMS CONTAINING MgO AND Fe2O3 WITH CaO,Al2O3 AND SiO2401

CaO-C2S-C5A3-C4AF401

CaO-C2S-C5A3-C2F409

The system CaO-C2S-C5A3-C2F modified by 5 per cent MgO412

Crystallization in polycomponent systems415

19.SYSTEMS CONTAINING K2O419

The alkalies419

K2O-CaO419

K2O-SiO2419

K2O-Al2O3421

K2O-CaO-Al2O3421

KA-C4AF-C2F423

K2O-CaO-SiO2425

C2S-KCS425

C3S-KA426

C2S-KA428

C3S-C2S-KA428

C3S-C2S-KA-Fe2O3428

KC23S12-CaO-C5A3429

KC23S12-MgO432

20.SYSTEMS CONTAINING Na2O AND Li2O AND THE ALKALIES WITH SO3433

Na2O-CaO433

Na2O-SiO2433

Li2O-SiO2433

Na2O-Al2O3433

KS-NS-SiO2434

NS-LS-SiO2434

NS-Fe2O3-SiO2435

Na2O-CaO-Al2O3435

Na2O-CaO-SiO2440

Na2O-CaO-Al2O3-SiO2441

CaO-C4AF-(NA3)446

Na2O-CaO-C5A3-C2F447

Na2O-CaO-C2S-CF448

Na2O-CaO-Al2O3-Fe2O3-SiO2449

KC23S12-CaSO4450

K2SO4 and Na2SO4 in clinker452

Effect of SO3 on the alkali compounds of clinker453

Ⅲ.The Chemistry of Cement Utilization461

21.EARLY STUDIES ON CEMENT HYDRATION463

The crystallization theory463

Hydration464

Crystallization464

Hardening466

Application to portland cement467

The colloid hypothesis471

Discussion of the crystallization and colloid theories473

The chemical nature of the setting and hardening processes482

Reactions of hydration482

Solid solutions483

Identification of phases484

The chemical significance of rate of set486

Introduction of retarders486

Solubility studies487

Alkali action488

Electrolytic effects489

Miscellaneous retarders491

22.THE SYSTEM CaO-SiO2-H2O495

The principles of hydrolysis and hydration495

Hydrolytic reactions of the calcium silicates496

Complete hydrolysis497

Hydrolytic equilibrium498

Interaction with excess of water500

Ionization constants502

Interaction at higher concentrations505

The pattern of phase equilibria508

Nomenclature of the calcium silicate hydrates508

Interaction of components509

Dehydration studies524

The chemical nature of the hydration products526

The CaOSiO2 relationship526

The water content528

Hydrothermal reactions529

Early investigations529

Later studies534

The structure of the hydration products538

23.SYSTEMS CONTAINING CaO AND H2O WITH Al2O3 AND Fe2O3543

Hydrolytic equilibria543

Action of water on the calcium aluminates545

Action of Ca(OH)2 solution on the calcium aluminates548

The calcium aluminate hydrates550

The C3A hydrates551

The C2A and C4A hydrates555

Equilibria in the system CaO-Al2O3-H2O559

The calcium ferrite hydrates562

Hydration of the alumina and iron compounds in steam564

24.THE ALUMINATE AND FERRITE COMPLEX SALTS571

Early history571

The calcium sulfoaluminates574

The calcium chloraluminates575

The calcium sulfoferrites579

The hydrogarnet solid-solution series579

The sulfoaluminate solid-solution series581

The system CaO-Al2O3-CaSO4-H2O582

The sulfoaluminate-alkali systems587

25.THE HEAT OF HYDRATION591

Heats of complete hydration592

Effects of composition593

Effect of glass content and other variables601

Comparison of methods603

26.THE STRUCTURE OF HYDRATED CEMENTS607

Microscopic structure of the hydrated compounds607

Tricalcium silicate608

Dicalcium silicate609

Tricalcium aluminate610

Tetracalcium aluminoferrite611

K2O·23CaO·12SiO2613

Mixed compounds and commercial cements613

Effect of gypsum613

Effect of saturated Ca(OH)2 solution614

Effect of alkali compounds615

Microscopic structure of cement pastes615

Physical characteristics of hydrated pastes623

Gel structure623

Adsorption studies624

Electron optics627

27.THE SETTING OF CEMENT PASTES647

Theories of the setting process647

Selective hydration647

Crystallization of hydration products649

Film formation653

Mutual coagulation656

False set658

The effect of gypsum660

Optimum gypsum content662

The effects of other materials664

Phase equilibrium in the presence of CaSO4666

28.THE HARDENING OF CEMENT PASTES669

The hydrolysis and hydration of cement pastes669

Hydration measured by depth of hydrated layer673

The soundness of pastes674

The effects of composition678

The effects of cooling rate683

The effects of steam treatment686

29.EXTERNAL REACTIONS OF HYDRATED PASTES691

Reactions with sulfate solutions692

The nature of sulfate corrosion692

The effects of steam curing694

The specific effects of the cement compounds695

The alkali-aggregate reaction700

The action of pozzolanas708

30.TESTS FOR CEMENT QUALITY715

Methods for predicting sulfate resistance716

Visual observation717

Strength change718

Length change720

Elastic modulus724

Methods of calculation726

Methods based on chemical action727

The formation of calcium sulfoaluminate727

A sulfate susceptibility test728

The water test for durability730

The disintegration index731

The sugar-solubility test732

Tracer studies of ion diffusion735

APPENDIXES738

1.X-Ray Powder Diffraction Patterns(d)of Clinker Components and Compounds738

2.X-Ray Powder Diffraction Patterns(d)of Cement Hydration Products744

3.Equations for Calculating Phase Composition of Clinker754

4.Effect of Various Substances on Concrete,and Protective Treatments,Where Required766

5.Miscellaneous Tables774

Conversion factors774

Molecular weight and percentage oxide composition of principal com-pounds of portland cement clinker(1954)775

AUTHOR INDEX777

SUBJECT INDEX783